System of systems for monitoring greenhouse gas fluxes

ABSTRACT

A system of systems to monitor data for carbon flux, for example, at scales capable of managing regional net carbon flux and pricing carbon financial instruments is disclosed. The system of systems can monitor carbon flux in forests, soils, agricultural areas, body of waters, flue gases, and the like. The system includes a means to identify and quantify sources of carbon based on simultaneous measurement of isotopologues of carbon dioxide, for example, industrial, agricultural or natural sources, offering integration of same in time and space. Carbon standards are employed at multiple scales to ensure harmonization of data and carbon financial instruments.

CROSS REFERENCE TO RELATED APPLICATIONS

The disclosure claims the benefit of the earlier filing date of U.S.Patent Application No. 61/149,122, filed on Feb. 2, 2009, the contentsof which is incorporated by reference herein in its entirety.

TECHNICAL FIELD

The disclosure relates generally to a geographic-scale standardizedsystem for the measurement, integration, and analysis of data forgreenhouse gas sources that can be used to support carbon trading andcarbon management policy.

BACKGROUND

The emergence of a market-based trading system for greenhouse gases(GHG) (e.g., IPCC 2007), specifically as embodied in atmospheric CO₂,presents a technically more demanding and project specific approachrelative to studies of the global carbon cycle (Tans et al., 1996;Steffen et al., 1998). Cost-effective, high precision and carbonspecific monitoring underpins not only our understanding of the carbondynamics of the planet (e.g., full carbon budget) but is also the basisof a new and rapidly emerging carbon economy with discretegeographically defined projects representing partial (local andregional) carbon budgets (Capoor and Ambrosi 2007). An accounting of thecarbon burden emitted at local, regional, country-wide and global scalesis mirrored in regulatory approaches to reduce, avoid and otherwisediminish current sources as well as show negative carbon results throughcarbon sequestration.

Specifically, the December 1997 Kyoto Protocol specified emissionstarget and timetables for industrialized nations and market-basedmeasures for meeting those targets (see Anderson, J. W. 1998, The KyotoProtocol on Climate Change: Resources for the Future) and the need toquantify carbon fluxes was needed to implement the Kyoto Protocol. WO99/42814 generally describes measurement of isotopes of CO₂ in order todetermine and monitor global and regional carbon emissions from naturaland anthropogenic sources. However, WO 99/42814 only described suchsystems in broad terms and did not provide any details regarding howspecific implementations should be carried out. Notably, even over adecade since the passage of the Kyoto Protocol, no experimental orcommercial system currently exists that combines systems for measuringand monitoring both ¹³C and ¹⁴C in one instrument. Particularly, noreliable and geographic-scale system for the direct measurement,monitoring, verification and accounting of carbon for the purposes ofcarbon trading is available since the introduction of the Kyoto Protocol(1997).

SUMMARY OF THE INVENTION

The present disclosure provides a system of systems allowing for thefirst time the integration of carbon flux from both natural and manmadecarbon emissions, producing a dual carbon accounting system in whichbiogenic or natural and fossil/industrial emissions are quantifiedseparately for the purposes of carbon trading. Thus, trading of carbonmay be refined as a two-carbon approach (e.g., fossil fuel C andbiogenic C), recognizing that both ecosystem function and anthropogenicactions may be differentially priced according to the efficiency ofcarbon reduction and other factors (e.g., ecological function) affordedby each at any given location and over any given time period. To-date,carbon pricing mechanisms do not account for the two types of carboneven though they are inter-connected reflecting man made and biogeniccarbon dynamics.

A system of systems is disclosed that allows for real time, quantitativeanalysis of isotopologues of atmospheric gases providing for componentidentification and quantification, such as carbon dioxide (CO₂), methane(CH₄) and nitrous oxide (N₂O). A system of systems is described thatcollects atmospheric gases, analyzes the gases for isotopic compositionusing isotopic analyzers and according to requirements for samplingfrequency, and harmonizes data across sampling sites using standardsand/or global references. Data are provided to a central location andprovide isotope-based data products according to specific embodimentsand use of conversion methods that result in metric tons of carbonappropriate for carbon trading exchanges. Such products in the case ofCO₂ can result in a two carbon system (e.g., biogenic and fossil carbon)for trading that can be applied by industries, states, regions,governments, greenhouse gas exchanges, verification bodies forgreenhouse gas treaties and by other stakeholders for use in carbonbudget analysis, carbon pricing and carbon management.

The disclosure also provides details for the design of a three celllaser system that is calibrated within the instrument, and also can beinter-calibrated with other instruments, e.g., across a landscape in atleast some instances, each instrument can be referenced to known globalstandards, ensuring geographic comparability of data, and thus monetaryequivalence when such data are used for carbon trading either as acontinuous live trading scheme or as a discontinuous trading scheme.Thus the disclosure represents capability far beyond the capability of asingle instrument for either ¹³C or ¹⁴C. Such single analysisdeterminations are currently the standard for the monitoring of carbonisotopologues and do not address the necessary components to understandnor use the data for purposes of carbon trading.

One aspect of the disclosure involves a system of systems to effectivelymeasure, monitor, report, verify, analyze and monetize data for sourceterms of greenhouse gases such as carbon budgets reflecting both fossiland biogenic carbon for a given area and over a given period of timewith a given frequency of sampling.

Another aspect of the disclosure provides an integrated, multi-isotoperatio instrument for the determination of the concentration and isotopicratios of one or more isotopologues of a component in a gas, such ascarbon dioxide in an ambient air stream. In certain embodiments,integrated, near-simultaneous multi-isotope ratio instrument for thedetermination of the concentration and isotopic ratios is provided.Relevant isotopologues include without limitation ¹²C, ¹³C and ¹⁴C; insome embodiments the measurement of the relevant carbon isotopologuesutilizes a three cell laser system.

Another aspect of the disclosure provides a field deployable instrumentcapable of near-simultaneous and precise measurement of theconcentration and isotope ratios of a component in a gas mixture drawnfrom any source, ranging from point sources such as a flue stack orextracted gas from the ocean, to open spaces of any kind over land orwater anywhere on Earth.

Another aspect of the disclosure provides a method employing the systemof systems to measure, monitor, identify, report, verify, analyze andmake available to carbon exchanges CO₂ emissions data based ongeographically discrete ensembles of analyzers for large areas offorest, agriculture, water bodies, natural preserves and otherwisenon-industrial sources, while providing for the same from industrial andother anthropogenic activities. Placements of such discrete ensemblesare determined by use of the system of systems in various initialconfigurations with selection of one or more preferred configurationsfor specified measurement and monitoring protocols. Thus, the system ofsystems is integral in determining the optimal application of the systemof systems; without such a system of systems no such effectivemeasuring, monitoring, verification and accounting of carbon can berealized. In the above cases, the disclosure provides for quantitativelydefining the fossil and biogenic contributions in a way that has notbeen reported.

Another aspect of the disclosure provides an instrument or groups ofinstruments capable of being controlled and queried remotely, as well asproviding data in real time via signal transmission to any number ofdata centers, control points or electronic greenhouse gas tradingplatforms.

Another aspect of the disclosure provides an instrument capable ofnear-simultaneous and multiple species analysis of isotopologues of agas that provides such analysis in a non-destructive manner with respectto the sample thus allowing the same gas stream to be used in additionalanalyzers of any type, including soil, dissolved inorganic carbon andother forms of carbon of interest. Such simultaneous analyses can beperformed on time scales of 1 second or less to hours depending on thetime constants of the biological and physical processes to be measuredand monitored.

Another aspect of the disclosure provides an instrument that can beexpanded to include a variety of other sensors and sampling technologiesas they become available and integrated within the three cell system.

Another aspect of the disclosure provides a method employing the systemof systems to measure, monitor, identify, report, verify, analyze andprovide to carbon exchanges CO₂ emission data for a variety of carbonemissions, ranging from industrial sources including discrete pointlocations, industrial complexes and over large areas of land where suchindustrial sources may be situated.

Another aspect of the disclosure includes employing one or moreuniversal sealed reference cells for each isotopologue such as ¹²C, ¹³Cand ¹⁴C ratios that are or can be made identical for each isotopologueand distributed uniformly within an ensemble(s) of instruments,providing for real time inter-comparability of measurements taken by allinstruments across time and space.

Still another aspect of the disclosure includes employing an ensemble ofinstruments across a defined area each with a sealed standard referencecell in which each instrument measures the isotope ratios of carbondioxide in the reference cell and in a stream of air or other gas and iscompared with other instruments in the ensemble and then with anexternal master reference gas sealed-cell (e.g. primary reference). Amaster reference gas sealed-cell may be maintained at a centralreference(s) facility ensuring comparability of isotopic data acrossspace and time in real time and providing verification for live carbontrading and monetization across all forms of financial settlementinvolving carbon derivatives. Such master reference gas sealed cellshall be linked to one or more international gas standards for ¹²C, 13Cand ¹⁴C ratios providing a network of inter-comparable data sets to beused for carbon trading, managing carbon budgets at a variety of scalesand to better understand the global carbon cycle.

Still another aspect of the disclosure includes the transmission ofisotopic data in real time via telemetry of any type to a central datacollection point where it is analyzed, aggregated and summarizedaccording to time and space coordinates that are then used as inputs inappropriate models. Such models and data result in a total mass ofcarbon emissions for a given area and time period providing market basedcarbon trading units such as metric tons of carbon.

Still another aspect of the disclosure includes generating an isotopebased equivalency for carbon emissions units, e.g., a two-carbon or dualcarbon accounting for biogenic and fossil derived carbon as means tomonetize with precision the carbon source amount, and to interface withgreenhouse gas exchanges or other trading mechanisms to support carbonpricing, trading and verification of the value of carbon based financialinstruments and compliance with carbon emissions regulatory frameworks.Such an interface could consist of models of the atmosphere, includingreal time meteorological, data, soil, oceans, specific ecosystems and ora variety of models with coupled components of the aforementioned types.The results of data-model fusion are actual mass of carbon fluxesdefined spatially and temporally that can be used to calculate carbonunits as metric tons for trading.

Still another aspect of the disclosure provides a method of deployingthe system of systems for measurement, reporting and verification ofcarbon emissions sources and quantities at discrete sites within afacility, or within local, regional, state, national and country-widelandscapes, or according to geographical treaty provisions, or acrossany land or water area on the surface, subsurface or airspace of theplanet Earth.

Still another aspect of the invention provides for a method to directlycompare ground-based and satellite-based measurements of carbon. In suchan embodiment, a satellite may house a sealed cell primary referencestandard as well as analytical devices to measure relevant portions ofthe light spectrum to detect carbon emissions. As the satellite passesover a region with an ensemble of multi-isotopic analyzers the satelliteborn sealed reference cell will ensure a single baseline for allanalyzers in the path of the satellite sensing spectrum, thus offering adirect, real time comparison between the two methods (e.g., groundbased, space based). This embodiment could also be used to verify and/orcorrect baseline features of ensembles whenever the satellite crossesthe geographic locations of multi-isotopic analyzers.

In various embodiments, the system of systems, components and relatedmethods may be used with a gas, liquid or solid sample, provided thatthe solid or liquid sample is first converted into a gas via heating,combustion or other suitable means. In certain embodiments, a method forproviding measurements of concentration and isotope ratio of a componentin a sample gas mixture, includes the following: A sample gas mixture isloaded into an instrument capable of measuring gas concentration andinto an instrument capable of measuring gas isotope ratio. Measurementsof gas concentration and gas isotope ratio are performed on said samplegas mixture. In some embodiments, the method further includes removingan interfering species from said gas mixture. In some embodiments, thecomponent of said sample gas mixture is carbon dioxide and saidinterfering gas species is oxygen. In some embodiments, the methodfurther includes increasing or decreasing the concentration of thecomponent, e.g., carbon dioxide, of the sample gas mixture in order toimprove the precision of the measurements. In some embodiments themeasurement of gas concentration and measurement of gas isotope ratioare performed substantially simultaneously in a three cell laser systemfor each of the relevant forms of carbon (¹²CO₂, ¹³CO₂, ¹⁴CO₂).

Certain embodiments provide an apparatus for providing measurements ofconcentration and isotope ratio of a component in a sample gas mixture.The apparatus includes a device for measuring concentration of thecomponent in the sample gas mixture; a device for measuring isotoperatio of the component in the sample gas mixture; and a means to loadthe sample gas mixture into the concentration measuring device and intothe isotope ratio measuring device. In some instances, the concentrationmeasuring device is an infrared gas analyzer. In some embodiments, theisotope ratio measuring device is a laser-based device. In someembodiments, the apparatus further comprises a means to remove one ormore interfering species from the sample gas mixture prior tomeasurement of the component. In some instances, the component of thesample gas mixture is CO₂ and the interfering species is oxygen. In someembodiments, the means to remove the interfering gas species comprisesone or more chemical scrubbers, or a gas selective membrane, or a meansto cryogenically separate the interfering gas species from the componentof said sample gas mixture. In some embodiments, the apparatus furthercomprises a means for increasing or decreasing the concentration of thecomponent of the sample gas mixture in order to improve the precision ofthe measurements. In some embodiments, the means for increasing theconcentration of the component comprises a gas selective membrane, or acryogenic trap, and the means to decrease the concentration comprisesdilution of a sample gas with an inert gas such as nitrogen within anexpandable control volume such as a stainless steel bellows. Certainembodiments provide an apparatus for providing simultaneous measurementsof concentration and isotope ratio for multiple species of carbon, forexample, the simultaneous measurement of the carbon 13 and carbon 14isotope ratios as compared to ¹²C, with a three cell laser system asreferred to above.

Certain embodiments provide a method or apparatus as described above foruse in a combined analytical system, wherein data results from thesystem are used to create, manage and monetize carbon budgets. In someinstances, the system includes a geographic network of devices. In someembodiments, the network covers a specific industrial site, a nation, astate, a region, a country, boundaries of greenhouse gas treaty ortreaties, or any other defined area selected for measuring andmonitoring. In some instances results are obtained over the area toreduce uncertainty in carbon trading. An anti-fraud means can beemployed to verify carbon emissions reductions by various entities.Means can be provided to comply with any voluntary or mandated emissionsreduction policy or to verify multi-national treaties for reduction incarbon emissions. In some embodiments, means are provided to reduceuncertainty in the transaction of any carbon based financial instrumentby replacing estimation of carbon emissions with actual real timemeasurements.

In still other embodiments, the system of systems may include externalsealed cell reference gases linked to international reference gases invarious configurations separated from field analyzers but used tocompare the primary standard with standards used in the field devicesvia any form of telemetry. In still other embodiments, an externalsealed reference cell can be space born in a satellite or space stationin which carbon emissions sensors in the satellite offer comparison withground based multi-isotopic analyzers on the ground that overlap withthe satellite ground footprint or to provide an additional reference gasfor all multi-isotopic analyzers that communicate and compare data asthe space-born reference signal passes over ensembles of multi-isotopicanalyzers.

Another aspect of the invention provides a predetermined, desired, oroptimal density of the analyzers and measurement frequency distributedthroughout the geographic region of interest for the particularapplication of interest. Measuring, monitoring, analysis, andverification of the carbon flux can provide further insights into theoptimal density of the analyzers and measurement frequency of theanalyzers.

In certain embodiments, system of systems for generating tradableproducts that separately quantify biogenic and fossil carbon in forestair is described. The system of systems can include a carbon datacollection for collecting carbon flux data in a forest and a dataprocessing system for converting the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes to tradable products that separately quantify biogenic andfossil carbon in the forest. The carbon data collection system forcollecting carbon flux data in a forest includes an array of analyzersplaced in predetermined representative locations throughout a forest,where each analyzer includes a ¹²C laser device, a ¹³C laser device, a¹⁴C laser device, a sample chamber to measure the individual amounts of¹²C, ¹³C, and ¹⁴C isotopes contained in a forest air sample, and a timerto allow measurements of¹²C, ¹³C, and ¹⁴C isotopes at a rate of at least1 Hz, or 10 Hz, or 50 Hz, or 100 Hz, a standard reference gas module forobtaining a standard reference baseline and calibrating the measuredamounts of the ¹²C, ¹³C, and ¹⁴C isotopes from each of said analyzersbased on the standard reference baseline and a telemetry device forsending measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the forest airto the data processing system.

In certain embodiments, a method for generating tradable products thatseparately quantify biogenic and fossil carbon in forest air isdescribed. The method includes (a) placing an array of analyzers atpredetermined representative locations throughout a forest, where eachanalyzer comprises a ¹²C laser device, a ¹³C laser device, a ¹⁴C laserdevice, and a sample chamber; (b) collecting forest air samples in thesample chambers of the analyzers and measuring the individual amounts of¹²C, ¹³C, and ¹⁴C isotopes contained in the samples at a rate of atleast 1 Hz, or 10 Hz, or 50 Hz, or 100 Hz; (c) obtaining a standardreference baseline with a standard reference gas module; (d) calibratingthe measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes from each of theanalyzers based on the standard reference baseline; (e) sending themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the forest air samplesto a data processing system; and (f) converting the measured amounts of¹²C, ¹³C, and ¹⁴C isotopes in the data processing system to tradableproducts that separately quantify biogenic and fossil carbon in theforest.

In certain embodiments, each analyzer includes a standard reference gasmodule so that a standard reference baseline can be obtained at eachanalyzer.

In certain embodiments, the system of systems further includes a globalreference system including a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a global reference sample cell to measure theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a globalreference sample, and a calibration system for standardizing themeasured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of thedata collection system based on said measured amounts of ¹²C, ¹³C, and¹⁴C isotopes contained in the global reference sample so that themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the forest air samplescan be standardized based on measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in a global reference sample. In certain embodiments, theglobal reference sample can be located in a satellite.

In certain embodiments, at least 25, 50, 75, or 100 analyzers are placedat predetermined representative locations throughout the forest.

In certain embodiments, the predetermined representative locationsinclude borders of discrete forest areas, wherein said borders include aregion, a state, a group of states, a border configuration defining agreenhouse gas treaty or other convention that requires monitoringgreenhouse gases.

In certain embodiments, the predetermined representative locationsinclude above the forest canopy, below the forest canopy and at theforest floor.

In certain embodiments, the data processing system can further includeone or more conversion systems parameterized for biogenic and fossilfuel carbon to convert the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the forest.

In certain embodiments, system of systems for generating tradableproducts that separately quantify biogenic and fossil carbon in soil isdescribed. The system of systems can include a carbon data collectionfor collecting carbon flux data in soil and a data processing system forconverting the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes totradable products that separately quantify biogenic and fossil carbon inthe soil. The carbon data collection system for collecting carbon fluxdata in a soil includes an array of analyzers placed in predeterminedrepresentative locations throughout the soil, where each analyzerincludes a ¹²C laser device, a ¹³C laser device, a ¹⁴C laser device, asample chamber to measure the individual amounts of ¹²C, ¹³C, and ¹⁴Cisotopes contained in a soil sample, and a timer to allow measurementsof ^(12C,) ¹³C, and ¹⁴C isotopes at a rate of at least 1 Hz, or 10 Hz,or 50 Hz, or 100 Hz, a standard reference gas module for obtaining astandard reference baseline and calibrating the measured amounts of the¹²C, ¹³C, and ¹⁴C isotopes from each of said analyzers based on thestandard reference baseline and a telemetry device for sending measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes in the soil to the data processingsystem.

In certain embodiments, a method for generating tradable products thatseparately quantify biogenic and fossil carbon in soil is described. Themethod includes (a) placing an array of analyzers at predeterminedrepresentative locations throughout a soil, where each analyzercomprises a ¹²C laser device, a ¹³C laser device, a ¹⁴C laser device,and a sample chamber; (b) collecting soil samples in the sample chambersof the analyzers and measuring the individual amounts of ¹²C, ¹³C, and¹⁴C isotopes contained in the samples at a rate of at least 1 Hz, or 10Hz, or 50 Hz, or 100 Hz; (c) obtaining a standard reference baselinewith a standard reference gas module; (d) calibrating the measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes from each of the analyzers basedon the standard reference baseline; (e) sending the measured amounts of¹²C, ¹³C, and ¹⁴C isotopes in the soil samples to a data processingsystem; and (f) converting the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the soil.

In certain embodiments, each analyzer includes a standard reference gasmodule so that a standard reference baseline can be obtained at eachanalyzer.

In certain embodiments, the system of systems further includes a globalreference system including a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a global reference sample cell to measure theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a globalreference sample, and a calibration system for standardizing themeasured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of thedata collection system based on said measured amounts of ¹²C, ¹³C, and¹⁴C isotopes contained in the global reference sample so that themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the soil samples canbe standardized based on measured amounts of ¹²C, ¹³C, and ¹⁴C isotopesin a global reference sample. In certain embodiments, the globalreference sample can be located in a satellite.

In certain embodiments, at least 25, 50, 75, or 100 analyzers are placedat predetermined representative locations throughout the soil.

In certain embodiments, the data processing system can further includeone or more conversion systems parameterized for biogenic and fossilfuel carbon to convert the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the soil.

In certain embodiments, the measured amount fossil carbon relative tothe measured biogenic carbon can indicate damage in the soil.

In certain embodiments, system of systems for generating tradableproducts that separately quantify biogenic and fossil carbon in anagricultural area is described. The system of systems can include acarbon data collection for collecting carbon flux data in agriculturalarea and a data processing system for converting the measured amounts of¹²C, ¹³C, and ¹⁴C isotopes to tradable products that separately quantifybiogenic and fossil carbon in the agricultural area. The carbon datacollection system for collecting carbon flux data in the agriculturalarea includes an array of analyzers placed in predetermined above-groundand sub-surface locations in an agricultural area, where each analyzerincludes a ¹²C laser device, a ¹³C laser device, a ¹⁴C laser device, asample chamber to measure the individual amounts of ¹²C, ¹³C, and ¹⁴Cisotopes contained in the above-ground and sub-surface location samples,and a timer to allow measurements of ¹²C, ¹³C, and ¹⁴C isotopes at arate of at least 1 Hz, or 10 Hz, or 50 Hz, or 100 Hz, a standardreference gas module for obtaining a standard reference baseline andcalibrating the measured amounts of the ¹²C, ¹³C, and ¹⁴C isotopes fromeach of said analyzers based on the standard reference baseline and atelemetry device for sending measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the agricultural area to the data processing system.

In certain embodiments, a method for generating tradable products thatseparately quantify biogenic and fossil carbon in an agricultural areais described. The method includes (a) placing an array of analyzers atpredetermined representative above-ground an sub-surface locations in anagricultural area, where each analyzer comprises a ¹²C laser device, a¹³C laser device, a ¹⁴C laser device, and a sample chamber; (b)collecting samples of carbon gas in the above-ground and sub-surfacelocations in the sample chambers of the analyzers and measuring theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in thesamples at a rate of at least 1 Hz, or 10 Hz, or 50 Hz, or 100 Hz; (c)obtaining a standard reference baseline with a standard reference gasmodule; (d) calibrating the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes from each of the analyzers based on the standard referencebaseline; (e) sending the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopesin the above-ground and sub-surface samples to a data processing system;and (f) converting the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes inthe data processing system to tradable products that separately quantifybiogenic and fossil carbon in the agricultural area.

In certain embodiments, the above-ground locations can include 0 to 20meters above the ground. In some other embodiments, the sub-surfacelocations can include 0 to 100 meters below the surface.

In certain embodiments, each analyzer includes a standard reference gasmodule so that a standard reference baseline can be obtained at eachanalyzer.

In certain embodiments, the system of systems further includes a globalreference system including a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a global reference sample cell to measure theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a globalreference sample, and a calibration system for standardizing themeasured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of thedata collection system based on said measured amounts of ¹²C, ¹³C, and¹⁴C isotopes contained in the global reference sample so that themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the agricultural areasamples can be standardized based on measured amounts of ¹²C, ¹³C, and¹⁴C isotopes in a global reference sample. In certain embodiments, theglobal reference sample can be located in a satellite.

In certain embodiments, at least 25, 50, 75, or 100 analyzers are placedat predetermined representative locations throughout the agriculturalarea.

In certain embodiments, the data processing system can further includeone or more conversion systems parameterized for biogenic and fossilfuel carbon to convert the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the agricultural area.

In certain embodiments, system of systems for generating tradableproducts that separately quantify biogenic and fossil carbon in a bodyof water is described. The system of systems can include a carbon datacollection for collecting carbon flux data in a body of water and a dataprocessing system for converting the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes to tradable products that separately quantify biogenic andfossil carbon in the body of water. The carbon data collection systemfor collecting carbon flux data in a soil includes an array of analyzersplaced in predetermined representative locations throughout the body ofwater, where each analyzer includes a ¹²C laser device, a ¹³C laserdevice, a ¹⁴C laser device, a gas stripping device capable of strippingdissolved gases from the body of water, a sample chamber to measure theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in dissolvedgas stripped from the body of water sample, and a timer to allowmeasurements of ¹²C, ¹³C, and ¹⁴C isotopes at a rate of at least 1 Hz,or 10 Hz, or 50 Hz, or 100 Hz, or at least once an hour, a standardreference gas module for obtaining a standard reference baseline andcalibrating the measured amounts of the ¹²C, ¹³C, and ¹⁴C isotopes fromeach of said analyzers based on the standard reference baseline and atelemetry device for sending measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the body of water to the data processing system.

In certain embodiments, a method for generating tradable products thatseparately quantify biogenic and fossil carbon in a body of water isdescribed. The method includes (a) placing an array of analyzers atpredetermined representative locations throughout a body of water, whereeach analyzer comprises a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a sample chamber, and a gas stripping device capableof stripping dissolved gases from the body of water; (b) collectingwater samples in the analyzers; (c) stripping dissolved gases from thewater samples; (d) collecting the gases in the sample chambers of theanalyzers and measuring the individual amounts of ¹²C, ¹³C, and ¹⁴Cisotopes contained in the samples at a rate of at least 1 Hz, or 10 Hz,or 50 Hz, or 100 Hz, or at least once an hour; (e) obtaining a standardreference baseline with a standard reference gas module; (f) calibratingthe measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes from each of theanalyzers based on the standard reference baseline; (g) sending themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the samples ofdissolved gases in the body of water to a data processing system; and(h) converting the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in thedata processing system to tradable products that separately quantifybiogenic and fossil carbon in the body of water.

In certain embodiments, each analyzer includes a standard reference gasmodule so that a standard reference baseline can be obtained at eachanalyzer.

In certain embodiments, the system of systems further includes a globalreference system including a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a global reference sample cell to measure theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a globalreference sample, and a calibration system for standardizing themeasured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of thedata collection system based on said measured amounts of ¹²C, ¹³C, and¹⁴C isotopes contained in the global reference sample so that themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the water samples canbe standardized based on measured amounts of ¹²C, ¹³C, and ¹⁴C isotopesin a global reference sample. In certain embodiments, the globalreference sample can be located in a satellite.

In certain embodiments, at least 25, 50, 75, or 100 analyzers are placedat predetermined representative locations throughout the body of water.

In certain embodiments, the data processing system can further includeone or more conversion systems parameterized for biogenic and fossilfuel carbon to convert the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the body of water.

In certain embodiments, the data processing system tracks the measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes over a period of time to monitorchange of nutrients in the body of water.

In certain embodiments, system of systems for generating tradableproducts that separately quantify biogenic and fossil carbon in fluegases is described. The system of systems can include a carbon datacollection for collecting carbon flux data from flue gases and a dataprocessing system for converting the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes to tradable products that separately quantify biogenic andfossil carbon in the flue gases. The carbon data collection system forcollecting carbon flux data from flue gases includes an array ofanalyzers placed in predetermined representative locations exposed toflue gases, where each analyzer includes a ¹²C laser device, a ¹³C laserdevice, a ¹⁴C laser device, a sample chamber to measure the individualamounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a flue gas sample,and a timer to allow measurements of ¹²C, ¹³C, and ¹⁴C isotopes at arate of at least 1,440 times a day, 1 Hz, or 10 Hz, or 50 Hz, or 100 Hz,a standard reference gas module for obtaining a standard referencebaseline and calibrating the measured amounts of the ¹²C, ¹³C, and ¹⁴Cisotopes from each of said analyzers based on the standard referencebaseline and a telemetry device for sending measured amounts of ¹²C,¹³C, and ¹⁴C isotopes in the flue gases to the data processing system.

In certain embodiments, a method for generating tradable products thatseparately quantify biogenic and fossil carbon in flue gases isdescribed. The method includes (a) placing an array of analyzers atpredetermined representative locations exposed to flue gases, where eachanalyzer comprises a ¹²C laser device, a ¹³C laser device, a ¹⁴C laserdevice, and a sample chamber; (b) collecting flue gas samples in thesample chambers of the analyzers and measuring the individual amounts of¹²C, ¹³C, and ¹⁴C isotopes contained in the samples at a rate of atleast 1,440 times a day, 1 Hz, or 10 Hz, or 50 Hz, or 100 Hz; (c)obtaining a standard reference baseline with a standard reference gasmodule; (d) calibrating the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes from each of the analyzers based on the standard referencebaseline; (e) sending the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopesin the samples of flue gas to a data processing system; and (f)converting the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in thedata processing system to tradable products that separately quantifybiogenic and fossil carbon in the flue gases.

In certain embodiments, each analyzer includes a standard reference gasmodule so that a standard reference baseline can be obtained at eachanalyzer.

In certain embodiments, the system of systems further includes a globalreference system including a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a global reference sample cell to measure theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a globalreference sample, and a calibration system for standardizing themeasured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of thedata collection system based on said measured amounts of ¹²C, ¹³C, and¹⁴C isotopes contained in the global reference sample so that themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the flue gas samplescan be standardized based on measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in a global reference sample. In certain embodiments, theglobal reference sample can be located in a satellite.

In certain embodiments, at least 25, 50, 75, or 100 analyzers are placedat predetermined representative locations exposed to flue gases.

In certain embodiments, the data processing system can further includeone or more conversion systems parameterized for biogenic and fossilfuel carbon to convert the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the flue gases.

In certain embodiments, the data processing system tracks the measuredamounts of ¹²C, ¹³C and ¹⁴C isotopes over a period of time to monitorreduction of combustion of fossil carbon in accordance with regulatoryor voluntary emission guidelines.

In certain embodiments, system of systems for generating tradableproducts that separately quantify biogenic and fossil carbon near anuclear power plant is described. The system of systems can include acarbon data collection for collecting carbon flux data from flue gasesand a data processing system for converting the measured amounts of ¹²C,¹³C, and ¹⁴C isotopes to tradable products that separately quantifybiogenic and fossil carbon near the nuclear power plant. The carbon datacollection system for collecting carbon flux data near a nuclear powerplant includes an array of analyzers placed in predeterminedrepresentative locations near a nuclear power plant, where each analyzerincludes a ¹²C laser device, a ¹³C laser device, a ¹⁴C laser device, asample chamber to measure the individual amounts of ¹²C, ¹³C, and ¹⁴Cisotopes contained in discharges of the nuclear power plant, and a timerto allow measurements of ¹²C, ¹³C, and ¹⁴C isotopes at a rate of atleast 1 Hz, or 10 Hz, or 50 Hz, or 100 Hz, a standard reference gasmodule for obtaining a standard reference baseline and calibrating themeasured amounts of the ¹²C, ¹³C, and ¹⁴C isotopes from each of saidanalyzers based on the standard reference baseline and a telemetrydevice for sending measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in thedischarges of the nuclear power plant to the data processing system.

In certain embodiments, a method for generating tradable products thatseparately quantify biogenic and fossil carbon near nuclear power plantis described. The method includes (a) placing an array of analyzers atpredetermined representative locations near a nuclear power plant, whereeach analyzer comprises a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a sample chamber; (b) collecting samples of dischargesof the nuclear power plant in the sample chambers of the analyzers andmeasuring the individual amounts of ¹²C, ¹³C, and ¹⁴C isotopes containedin the samples at a rate of at least 1 Hz, or 10 Hz, or 50 Hz, or 100Hz; (c) obtaining a standard reference baseline with a standardreference gas module; (d) calibrating the measured amounts of ¹²C, ¹³C,and ¹⁴C isotopes from each of the analyzers based on the standardreference baseline; (e) sending the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes in the samples of discharge of the nuclear power plant to adata processing system; and (f) converting the measured amounts of ¹²C,¹³C, and ¹⁴C isotopes in the data processing system to tradable productsthat separately quantify biogenic and fossil carbon in the discharges ofthe nuclear power plant.

In certain embodiments, each analyzer includes a standard reference gasmodule so that a standard reference baseline can be obtained at eachanalyzer.

In certain embodiments, the system of systems further includes a globalreference system including a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a global reference sample cell to measure theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a globalreference sample, and a calibration system for standardizing themeasured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of thedata collection system based on said measured amounts of ¹²C, ¹³C, and¹⁴C isotopes contained in the global reference sample so that themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the discharges of thenuclear power plant can be standardized based on measured amounts of¹²C, ¹³C, and ¹⁴C isotopes in a global reference sample. In certainembodiments, the global reference sample can be located in a satellite.

In certain embodiments, at least 25, 50, 75, or 100 analyzers are placedat predetermined representative locations near the nuclear power plant.

In certain embodiments, the data processing system can further includeone or more conversion systems parameterized for biogenic and fossilfuel carbon to convert the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the discharges of thenuclear power plant.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a summary graph of the concentrations of ¹⁴CO₂, ¹³CO₂ and CO₂concentration spanning the years 1850 to 2000, as derived from a varietyof sources (Kosovic 2008).

FIG. 2 is a plot of ¹³C versus ¹⁴C isotope ratios for gaseous emissionsof fossil fuels, modern plants and analyses of liquid biofuels withvarying concentrations of petrochemical fuels. The ¹³C versus ¹⁴C datarepresent relevant source terms in the biosphere reflecting both fossilfuel and biogenic carbon sources as follows. Biodiesel blends (diamonds)(Reddy et al., 2008); Values for natural gas, liquid fuels and coal(filled squares) (Widory 2006); Modern grasses (solid bar) (Riley etal., 2008); Modern maize (filled inverted triangle) (Hsueh et al.,2007); Modern air (oval) (Levin et al., 2003); Open box representingrange of modern C4 plants (O'Leary, 1988); Open box representing rangeof modern C3 plants (O'Leary, 1998); Solid box representing magmatic CO₂(Mary & Jambon, 1987); Open triangles represent soil CO₂ from tree killand normal tree sites in the Mammoth Mountain area (Farrar et al.,1995).

FIG. 3 is an illustration of the wavelengths of excitation for nineisotopologues of CO₂. The arrows represent the lasing transitionsemployed for determination of isotope ratios for ¹⁴C¹⁶O₂ 101, ¹³C¹⁶O₂102 and ¹²C¹⁶O₂ 103.

FIG. 4 is a block diagram representing modules of a system according tocertain embodiments.

FIG. 5 is an illustration of the typical environments in which isotopicanalyses can be carried out for the purposes of quantifying carbonemissions from the dominant sources for the gas to be used for carbontrading.

FIG. 6 is a summary block diagram of an apparatus according to certainembodiments. The following reference numerals will be used in FIGS. 6through 11.

-   2 gas-tight inlet tube-   4 infrared gas analyzer-   5 gas-tight coupling tube-   6 electrical connection-   7 gas-tight coupling tube-   8 microprocessor-based data acquisition unit-   9 gas-tight coupling tube-   10 electrical connection-   11 electrical connection-   12 electrical connection-   14 self contained power supply unit-   15 weather hardened container-   16 electrical connection-   18 sample conditioning unit-   20 electrical connection-   22 electrical connection-   24 isotope ratio analyzer-   26 electrical connection-   28 electrical connection-   29 coupling tube-   30 diaphragm pump-   33 vent tube-   34 gas inlet tube-   36 oxygen scrubber-   38 gas outlet tube-   40 gas inlet tube-   42 gas-tight gas chamber-   44 gas-tight coupling tube-   46 gas selective membrane-   48 gas-tight coupling tube tee-   50 pure nitrogen source-   52 gas-tight coupling-   54 flow controlling valve-   56 gas outlet tube-   58 gas-tight coupling tube-   60 vacuum compatible solenoid valve-   62 gas-tight coupling tube-   64 gas-tight inlet tube-   66 vacuum compatible solenoid valve-   68 gas-tight coupling tube tee-   70 gas-tight coupling tube-   72 solenoid valve-   74 pure nitrogen source-   76 four-port, two position flow switching valve-   78 coupling tube-   80 coupling tube-   82 cryogenic trap-   84 gas outlet tube-   86 coupling tube-   88 stainless steel lid-   90 disc-   92 gas-tight electrical feed-through-   94 open end of U tube-   98 open end of U tube-   100 stainless steel vent tube-   102 solenoid valve-   104 gas exhaust tube-   106 fiberglass-insulated resistance heating wire-   108 stainless steel “U” tube-   110 stainless steel cylinder-   112 liquid nitrogen dewar-   113 sample chamber for unknown measurement (ZnSe windows)-   114 carrier gas cylinder or generator-   115 stainless steel expandable bellows-   116 sample inlet-   117 capillary tubing to regulate gas flow into the sample cell

FIG. 7 is a block diagram of an embodiment of a sample conditioning unitas incorporated in the apparatus of FIG. 6.

FIG. 8 is a block diagram of another embodiment of a sample conditioningunit as incorporated in the apparatus of FIG. 6, such sampleconditioning unit utilizing a gas selective membrane.

FIG. 9 is a block diagram of an embodiment of a sample conditioning unitas incorporated in the apparatus of FIG. 6, such sample conditioningunit utilizing a cryogenic trap.

FIG. 10 is a schematic cross-sectional view of an embodiment of acryogenic trap as incorporated in the sample conditioning unit of FIG.8.

FIG. 11 is a block diagram of an embodiment of a sample conditioningunit as incorporated in the apparatus of FIG. 6, such sampleconditioning unit utilizing an appropriate source of carrier gas, suchas nitrogen, to provide for dilution of a given sample to increase theaccuracy and precision for measurement of ¹³C and ¹⁴C in a sample.

FIG. 12 is a schematic of sealed reference cells consisting of analyzerinstrument reference cells, external primary or global reference cellsand satellite born 609 reference cells for ¹³CO₂ 606, ¹⁴CO₂ 608 and amixture of ¹³CO₂ and ¹⁴CO₂ 607. Sealed reference standards for ¹⁴CO₂comprising a set of global standards for which other laboratories haveobtained data could range from 100% fraction modern ¹⁴CO₂ 600 to 0.5%fraction modern 601 to 0% fraction modern 602. Sealed reference cellsfor ¹³CO₂ may consist of ¹³C isotope ratios of −25 per mil 603, −5.00per mil 604, and +10 per mil 605. Each primary or global referencesealed cell is made such that all sealed cells for a particular isotopiccomposition are identical (610, 611, 612), thus ensuring comparisonbetween analyzers in an ensemble and across ensembles wherever they maybe located.

FIG. 13 is a schematic of a three cell laser system for ¹²C, ¹³C and ¹⁴Cmeasurements according to certain embodiments utilizing three lasersystems, a detection system and reference and standard hardware.

FIG. 14 is a schematic of one embodiment of the sample operationsequence of a three-celled system according to the needs for samplevolume increase or decrease such that calibration curves, primaryreferences and external satellite references can be used for optimalmeasurement of the ¹²C/¹³C and ¹⁴C composition of a gas sample. A gassample 300 enters the analyzer where the concentration of ¹²C, ¹³C and¹⁴C are determined 301. If the concentration of ¹³CO₂ and/or ¹⁴CO₂ istoo low 302 a cryogenic trap (referring to FIG. 10) may be used toconcentrate these species, or if the concentrations are too high 302 foroptimal measurement, a bellows assembly (referring to FIG. 11) isutilized to dilute the original sample with carrier gas. Followingsample size adjustment a calibration curve for ¹⁴C 303 and for ¹³C 308is selected to ensure that the unknown sample concentration is withinthe range of the calibration curve. In addition, a primary reference gascan be measured to check the function of the ¹⁴C measurement 304 and the¹³C measurement 309. Primary reference gases 304, 309 are preferablycontained in sealed cells within the analyzer and represent the sameconcentration of ¹³C and ¹⁴C in all such primary reference cells of allanalyzers such that comparisons between individual analyzers and amongdifferent groups of analyzers is assured. An additional check onanalyzer function and comparability can be carried out by furthermeasurements utilizing an external reference cell for ¹⁴C 305 and ¹³C310. Both 305 and 310 are ideally located in an external reference gasmodule that is not equipped for analysis of unknowns, is accessible inreal time via telemetry and may be located in one or more areas whereensembles of analyzers are placed. 305 and 306 as external sealed cellreference gases are ideally the same for each isotopic species andpreferably have been measured in many laboratories around the world,thus comprising a global reference gas that allows other data sets to belinked directly to data sets resulting from utilization of themulti-isotopic analyzer. Such external global reference gas comparisonsprovide an additional criteria to ensure comparability across all suchinstruments and/or can be utilized to make adjustments to data sets withknown values of the said reference gases. In addition, an externalreference gas comparison may be carried out via satellite operation ofsaid sealed reference gases for ¹³C 311 and ¹⁴C 306 such that when thesensor beam of the satellite passes over one or more of multi-isotopicanalyzers an immediate comparison between ground based analyzers andspace based sensors can be carried out. Sample gas is expelled from theanalyzer 307, 312, or is re-routed for a repeat analysis. Repetition ofanalyses may be valuable to further characterize results for ¹³C and ¹⁴Callowing statistical data to be collected to better determine accuracyand precision of the analyzer.

FIG. 15 is an illustration showing instrument, location and instrumentinter-comparison overview and organization according to certainembodiments for a single device 100, devices with reference cell andtelemetry antenna 102, an array of selected devices 103 and an array ofselected devices with inter-comparison and inter-comparability options104 and reference to an external primary reference (PR) standard 105.Additional external standards may also be incorporated in an analyticaldesign as required to ensure comparability across instrument and acrossensembles.

FIG. 16 is an illustration of an embodiment showing an array ofinter-calibrated devices covering a specific geographic area 105,transmitting inter-calibrated data from each device via satellite orother wireless means 106, 107 to a central data and model analysiscenter 108.

FIG. 17 is an illustration of an embodiment showing ensembles ofinter-calibrated devices 900 covering three geographic regions acrossthe Earth (L1, L2, L3). The three ensembles are comprised of 9individual analyzers that are inter-calibrated within an ensemble andacross ensembles utilizing inter-calibration routines (referring to FIG.14), selected separate reference gases 901, primary reference gasesand/or global reference gases (referring to FIG. 14) 902 and optionallyembodied in a separate reference gas module and, optionally, as embodiedin a satellite that is used for measuring and monitoring greenhousegases from space 908. Data telemetry can be carried out by any wirelessmeans 904 including a communication satellite 903. 903 relays real timedata from the inter-calibrated analyzers 900, reference and/or globalreference cells data 901, 902 to data centers and carbon tradingexchanges 906 recognizing that reference cells 901, 902 may have thesame or different compositions of ¹³C and ¹⁴C (referring to FIG. 12) asrequired depending on technical factors related to the analyzers,calibration routines and inter-calibration routines. In one embodimentsuch data and communications are near instantaneous providing for anelectronically live carbon exchange platform 906. Data from analyzersmay also be compared with greenhouse gas sensing satellite data obtainedfrom space 907 offering additional verification of such data.

FIG. 18 shows a diagram of a data/model center 109 according to certainembodiments producing integrated model output for specified regions atspecified levels of aggregation 110, 111. This leads to translation ofdata into carbon units for trading such as metric tons CO₂ toappropriate carbon based exchanges 112, 113. The data can be accessed ina live-market (e.g., instantaneous) or on a less frequent basisaccording to type of carbon represented, such as biogenic carbon (e.g.,forest carbon) versus industrial fossil fuel based carbon, and accordingto trading protocols for a specific exchange.

FIG. 19 shows a summary of the main component processes of the system ofsystems for a given geographic area 401, a given time period 402, withinstruments 400 and data from samples measured by analyzers 406, groupsor ensembles of analyzers 400 and data ensembles 406, shared calibrationand inter-calibration protocols 403, global reference protocol 404 andexternal satellite based standards 405. All data are transmitted viawireless or other means of telemetry 407 to data centers that manage andincorporate the data 408 in one or more models 409 that ultimately areconverted to metric tons of biogenic or fossil fuel derived carbon 410.Such units can be registered and other administratively handled 411 forsale on an appropriate greenhouse gas trading exchanges, platforms, etc.412.

FIG. 20 shows an example of inter-calibration architecture resulting ina ¹³C data set (panel A) 801 from the analyzers 804, 805, 806 and 807(panel B). The analyzers 804, 805, 806 and 807 are placed in discretelocations (panel C). Analyzers 804, 805, 806 and 807 may also beintegrated with an optional external reference and/or global referencegas module 809 to ensure comparability across instruments in time andspace.

FIG. 21 shows an example of SCADA communication and network architecturefor data transmission from individual or grouped isotopic analyzers,comparison with optional external primary reference standard, collectionof such data by a master host and subsequent transmission to carbonexchanges.

FIG. 22 shows hypothetical partial carbon budgets, their nestedstructure (panel A) and exemplary model results (panel B) for dualcarbon accounting.

FIG. 23 shows an example of a use of the system of systems to measure,report, verify and provide for carbon exchanges within an array ofdevices placed in a forest setting over 2.5 years according to season.Hypothetical carbon fluxes for CO₂ total concentration, ¹³CO₂ and ¹⁴CO₂ratios are also shown.

FIG. 24 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges across the continentalUS. Optional external primary reference standards may used according tostate, regional and continental reporting goals.

FIG. 25 shows an example of the use of a system of systems to measure,report, verify and provide for carbon emissions data for the state ofMaine. Optional primary reference standards may be used as needed.

FIG. 26 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges for the RegionalGreenhouse Initiative (RGGI) including the states of, Connecticut,Delaware, Maine, Maryland, Massachusetts, New Hampshire, New Jersey, NewYork, Rhode Island and Vermont. Optional external reference standardsmay be used as needed.

FIG. 27 shows an example of the use of the system of systems to measure,report, verify and provide for carbon exchanges for the MidwestGreenhouse Gas Accord (2009) including the states of Iowa, Illinois,Kansas, Manitoba (Canada), Michigan, Minnesota and Wisconsin. Optionalexternal reference standards may be used as needed.

FIG. 28 shows an example of the use of the system of systems to measure,report, verify and provide for carbon exchanges for the Western ClimateInitiative including the states of Washington, Oregon, California,Montana, Utah, Arizona, New Mexico, British Columbia (Canada), Manitoba(Canada), Ontario (Canada) and Quebec (Canada). Optional externalreference standards may be used as needed.

FIG. 29 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges for the European UnionExchange Trading Scheme including the countries of Austria, Belgium,Czech Republic, Estonia, France, Hungary, Germany, Greece, Ireland,Italy, Latvia, Lithuania, Luxemborg, Malta, Netherlands, Poland,Slovakia, Slovenia, Spain, Sweden, UK, Norway, Iceland and Lichenstein.Optional external reference standards may be used as needed.

FIG. 30 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges for soil carbonemissions. Optional external reference standards may be used as needed.

FIG. 31 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges for agriculturalactivities. Optional external reference standards may be used as needed.

FIG. 32 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges for oceanic exchange.Optional external reference standards may be used as needed.

FIG. 33 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges on a city wide scalerepresenting the city of New York, N.Y., USA. Optional externalreference standards may be used as needed.

FIG. 34 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges for CO₂ sequestrationprojects. Optional external reference standards may be used as needed.

FIG. 35 shows an example of the use of a system of systems to measure,report, verify and provide for carbon exchanges for flue gas. Optionalexternal reference standards may be used as needed.

DETAILED DESCRIPTION Long Recognized Needs for Direct Measuring andMonitoring of Carbon Emissions Not Met

Currently, carbon emissions as gaseous carbon dioxide are largelyestimated from a variety of secondary data including amount of fuelburned, combustion efficiencies and economic data. Carbon inventories,required under the United Nations Framework Convention on ClimateChange, are self-reported and essentially un-verified (Ellerman andJoskow 2008). Actual measurements of total carbon dioxide in theatmosphere are made by a number of stakeholders but do not reveal thesource or type of emissions and may not be directly tied to individualsources of CO₂ which are varied in origin and magnitude (e.g., oceanic,forests, industry, carbon capture and storage). Indeed, the level ofmonitoring and appropriate technologies needed to integrate emissionsdata to support financial markets were not envisioned in the pre-Kyotoperiod of regulatory compliance. The brief history of the European UnionEmissions Trading Scheme (Convery and Redman 2007) has shown that directmeasuring, monitoring, reporting, verification and monetizationrequirements have not been successfully met as evidenced by pricefluctuations, difficulties in placing caps and recognition thatestimates of emissions fluxes can be as high as 10% of total emissions(Kosovic, 2008) and potentially much higher at sub-continental scalesand sub-annual scales (e.g., Turnbull et al., 2006). Moreover, the Kyotoaccord was not designed to incorporate carbon flux from natural sources,such as the world's forests and oceans, with industrial emissions, dueto an inadequate measuring, monitoring and reporting network for CO₂flux that requires diagnostic carbon species representing ecosystemfunction. Thus, even though the importance and need for measuring andmonitoring large scale carbon exchange, such as carbon sequestration inforests, has long been acknowledged, no such system is in place. Undercurrent operating protocols direct measurements of carbon emissionsresulting from fossil fuel combustion or from natural biogenic sourcesare not used to enforce treaty provisions or to quantify the potentialof forest carbon sequestration.

Both sides of the emerging carbon markets (e.g., bid (buyer) and ask(seller)) require quantification of the traded carbon entity forcredible pricing and market support while global scale data are requiredto assess the effectiveness of carbon markets as a response to climatechange and uncertainties in biospheric performance (e.g., Canadell etal., 2007; Raupach et al., 2007, US Climate Change Science Program2007). Thus, effective multi-scale measuring and monitoring would be anindependent means to verify Kyoto commitments as specified by the KyotoProtocol or by other protocols, greenhouse gas treaties or conventions(e.g., Regional Greenhouse Gas Initiative 2009), to integrate carbonbudgets across the landscape, as well as quantify carbon flux ofplanetary surfaces within the region of carbon management. However,despite a long standing need and the recognized importance of such amonitoring system, no scalable carbon accounting system based on directmeasurement is available.

Potential of Rare Forms of Carbon to Meet Measuring and Monitoring Needs

Rare forms of carbon, namely, ¹³C and ¹⁴C, are key to differentiatingbiogenic from fossil derived CO₂ yet these rare forms of carbon are notwidely used due to difficulty in making rapid, reliable, comparable andverified measurements. Rare forms of carbon are diagnostic by virtue oftheir concentrations in CO₂ and in the manner in which these forms arefractionated by biological and physical processes (Keeling 1979; Gravenet al., 2009). A means to making reliable and comparable measurements ofthe rare forms of carbon widespread in the planetary environment (e.g.,field sites worldwide) would provide a foundation for quantitativecarbon metrics through time and space and the basis for carbon pricingand trading.

While concentrations of CO₂ can be measured with high precision and arewidespread, now represented by some 252 stations from 57 countries (WMO2009; Peters et al., 2007).concentration measurements alone do notprovide a full deconvolution of the sources and sinks of this greenhousegas. Thus, an intrinsic partial carbon accounting creates uncertainty inresulting budgets used to assess project performance, placing caps (forcap and trade routines) and ultimately determination of the pricing ofcarbon in a variety of markets. However, rare forms of carbon,specifically carbon isotopes, intrinsic to and embedded in carbondioxide dynamics at all scales in the biosphere and atmosphere offer ameans to identify specific carbon dioxide sources, such as from fossilfuels, as well as provide data on the functioning of the natural carboncycle within a defined landscape. The data representation and data rate(e.g., continuous, daily, weekly, monthly) for the rare forms of carbon,such as ¹³CO₂ and ¹⁴CO₂, are minimal in comparison to CO₂ concentrationdata (Tans et al. 1996); ¹⁴CO₂ data are particularly limited.

Although determination of the isotopologues of CO₂ (¹³C, ¹⁴C) can offervaluable constraints on relevant carbon source/sink terms (e.g., Tans etal., 1996; Turnbull et al., 2010; Graven et al., 2009; Riley et al.,2008), a feasible “system of systems” required to measure, monitor,report, verify, account and manage carbon budgets and related financialinstruments based on actual measurements of carbon isotopologues is notavailable. Rather, isotopologues are typically individually acquired atspecific locations using different instrumentation and methods. They aredetermined primarily by discrete single analyses of flask samples thatare subsequently analyzed by high vacuum magnetic sector isotope ratiomass spectrometers (IRMS) at considerable cost and time (e.g., Tans etal., 1996; Vaughn et al., 2010). Or, in the case of atmospheric ¹⁴CO₂analyses, such analyses are performed using a variety of β-emitterdetectors and accelerator mass spectrometers (AMS) according to samplesize and treatment (e.g., Stork et al., 1997; Tuniz 2001).

Direct, rapid (e.g., range from sub-second data to longer as required))and widespread measurement of ¹⁴C in atmospheric CO₂ would provideunequivocal and quantitative data for fossil fuel sources. Such analysescould be linked to internationally recognized standards representingstandard reference material (e.g., Stuiver and Polach 1977), for use asprimary standards as well as global reference frameworks for ¹⁴CO2 and¹³CO₂ (Boaretto et al., 2002; Vaughn et al., 2010). The composition ofthe atmosphere with respect to ¹³CO₂ and ¹⁴CO₂ is well understood from aglobal perspective as reflected in the Seuss Effect (Levin et al., 1989;1995; Keeling 1979), however, widespread analysis of ¹⁴CO₂ will serve asindependent verification of fossil fuel based emissions on a variety ofscales, particularly at local and regional scales important to trackemissions from specified areas (Turnbull et al., 2006). The largedifference in the natural abundances of the rare forms of carbon (e.g.,¹³C 1.1%; ¹⁴C 10⁻¹⁰%) are reflected both in the instrumentation used,the difficulty of making reliable measurements and the data rate foreach species. The data rate or sampling rate (e.g., number of samplesper day or samples per second) for high precision ¹³C and ¹⁴Cmeasurements is quite small compared to data collected for total CO₂concentration, resulting in far too few measurements to support carbontrading. Thus, despite the long-felt need and established scientificvalidity of isotopic measurements, there are no widely distributed andintegrated analyzers upon which to base a method or methods to directlylink carbon emissions data with carbon trading and carbon management.

Thus, a system that offers direct, rapid, simultaneous, multi-scale andmulti-isotopic analytical capability for the important isotopologues of¹³C and ¹⁴C, and that could operate in the field on a continuous or nearcontinuous basis, would be a highly valuable system to measure, monitor,report, verify, account for and manage carbon budgets, carbon tradingand planetary climate change. To date, isotopic data have not been usedto measure or monitor carbon emissions for the purposes of carbontrading, or to support the use of current carbon or related greenhousegas financial instruments, or to assess compliance with eitherregulatory or voluntary emissions frameworks, despite a clear and wellrecognized need for such a system (UNFCC 2009).

According to a study conducted by the Lawrence Livermore NationalLaboratory (Kosovic et al., 2008), uncertainties in fuel consumption andoxidation efficiencies, representing the main sources of fossil fuelbased CO₂, are estimated to be at least ±10%. In the context of the 2008dollar volume of carbon traded at $129US billion, the uncertainty couldreach ±12.9 billion dollars. Thus, a system of systems that could reduceeconomic uncertainty would be highly valuable to stakeholdersrepresenting buyers and sellers of carbon credits, and assurepolicymakers and the public that carbon based trading systems aremanaged properly, are transparent and stable and can be protected fromfraud. While it is widely recognized that such a system of systems isneeded to reduce economic uncertainty and replace estimation with directmeasurement, no such system has been devised or is currently operating.

Carbon Budgets Deconvolution of Carbon Budgets Using Isotopic Forms ofCarbon

Fossil fuel emissions and the resultant changes in carbon budgets arethe focus of the Kyoto Protocol mechanisms (e.g., IPCC 2008) and othercarbon trading exchanges and platforms. They are the basis for carbontrading and carbon based financial instruments in the EU and theemerging voluntary markets in the US, such as the Chicago ClimateExchange (CCX 2009). Carbon budgets are difficult to construct withoutinformation about component sources. Since total CO₂ as commonlymeasured does not provide source or component information, it is clearthat isotopic data for the rare forms of carbon as discussed above wouldbe highly valued and of importance in measuring, monitoring, verifyingand accounting for fossil fuel emissions.

With respect to carbon 13, this isotope alone does not distinguishfossil fuel CO₂ from natural CO₂, thus making it impossible to determineeither with this isotope alone. The dilution of atmospheric ¹⁴CO₂ withfossil fuel derived CO₂ is well known and understood. FIG. 1 (adaptedfrom Kosovic et al., 2008) shows a graph spanning the years 1850 to 2000for measurements of ¹⁴CO₂ (squares), ¹³CO₂ (filled circles) and theatmospheric concentration of CO₂ (small open circles) derived from treerings, ice cores and the modern atmosphere, respectively. The decreasein ¹⁴CO₂ in the atmosphere over this period is directly related tofossil fuel additions linked to increasing CO₂ concentrations of theatmosphere. The half life of ¹⁴C is approximately 5730 years making itan ideal, direct and sensitive tracer for fossil based CO₂ emissions.Fossil fuel does not contain ¹⁴C, having long since naturally decayedduring the millions of years of coal and natural gas formation. Thus,the addition of fossil fuel CO₂ devoid of ¹⁴C strongly dilutes themodern ¹⁴C background, which is comprised of natural ¹⁴C production(Libby et al., 1949) and of ¹⁴C released from atomic bombs (Randerson etal., 2002). The ¹³CO₂ record, shown also as decreasing, is also linkedto the fossil fuel record, because plant-based fossil fuels (e.g., coaland natural gas) are depleted in ¹³C with respect to the atmosphere.Measurement of ¹⁴CO₂ concentration of the atmosphere to 2 per mil (‰)precision allows model calculation of about 2 ppm fossil fuel CO₂,within a background of 380 ppm, thus defining the fossil fuel input fora given source (Kosovic et al., 2008; Graven et al., 2009; Riley et al.,2008). The graph also clearly shows that ¹³C alone cannot differentiatefossil fuel carbon from biogenic carbon.

Thus, recognizing that ¹⁴C measurements and ¹³C measurements are rare incomparison to total CO₂ measurements, an apparatus and system of systemsfor ¹³C and ¹⁴C with acceptable precision and sensitivity to effectivelytrack isotopes in relation to fossil fuel and biogenic emissions in realtime is clearly needed and long sought as an important method forverification of fossil fuel emissions and treaty provisions atmeaningful spatial scales for management and monetization. However nosuch system is available or operating.

The value of using both ¹³C and ¹⁴C measurements is illustrated in FIG.2. The figure shows carbon 13 (y-axis) versus carbon 14 (x-axis) isotoperatios, published as indicated in the detailed descriptions of theFigures. It is observed that modern plants of the C3 type (representingmost plants and trees) and fossil fuels and emissions thereof overlapalmost entirely with respect to carbon 13 ratios (−20 to −38 per mil,FIG. 2). However, the ¹⁴C data clearly separate modern from fossil fuelsources with a range from −1000 Δ¹⁴C per mil, representing 100% fossilfuel carbon, to approximately +50 per mil, representing modernbackground ¹⁴C. Specifically, the value for carbon 13 derived from coalis very similar to that for modern C3 gases in ¹³C, but clearlydifferent in ¹⁴C ratios. As fossil fuel sources are devoid of ¹⁴Ccontent, all of these sources unequivocally are at 0% ¹⁴C or register as−1000 Δ¹⁴C per mil when analyzed. Moreover, one can see that carbonemissions from industrial fuels including natural gas and coal aresomewhat distinguishable one from the other based on ¹³C but not ¹⁴C.Automobile produced CO₂ carbon isotope ratios are also distinct incarbon 13 but not in carbon 14 ratios as indicated by the fossil andmodern brackets shown on the graph. Thus, a system of systems capable ofmeasuring both ¹³C and ¹⁴C composition would be valuable for determiningfossil and biogenic components of any gas stream that can be analyzed.For example, biofuel blend compositions (Reddy et al., 2008),increasingly mandated for power production facilities, can be readilyverified as to advertised biogenic/fossil fuel compositions (note thediamond symbols in FIG. 2). Thus, a system of systems that provided forthe differentiation of fossil fuel derived CO₂ and natural or biogenicCO₂ would fulfill a long standing and much sought after system tomeasure, monitor, verify and account for fossil fuel emissions and thepotential effects of such emissions on natural ecosystems. However, nosuch system exists or is currently operating.

Further, one can see that ¹³C and ¹⁴C ratios can be used to identifysources of natural CO₂ in cases where C4 plants (O'Leary 1998) (¹³Cvalues range from −19 to −11 per mil, FIG. 2) versus C3 plants areconcerned (O'Leary 1998). C4 plants are common in dry, arid areasrepresentative of plains and other non-forested areas. Such adistinction would be useful in the monitoring of many ecosystems of theworld where evidence of carbon release or uptake by the biosphere inrelation to rainfall and shifting C3 versus C4 composition couldestablish regional climate change forecasts, including in which areascarbon is a sink or a source of CO₂ and vice-versa. However, despite therecognized importance of monitoring of such changes in carbon uptake orrelease, there are no systems of systems currently in use that directlymeasure such changes.

An additional feature of the graph shown relates to the assessment ofecosystem function as influenced by carbon emissions. The data shownfrom Mammoth Mountain, a known and well studied area where naturalmagmatic CO₂ is released, represented by open triangles, clearlydelineate soil CO₂ associated with tree death from soil CO₂ in areas ofnatural ecosystem function. The Mammoth Mountain data clearly show thatusing both ¹⁴C and ¹³C data to monitor ecosystem function, aspotentially affected by release of CO₂ from large scale projects thatcapture and store CO₂ underground, is an effective and sensitive meansto measure, monitor, verify and account for such emissions to be usedfor carbon credits. Carbon capture and storage is viewed widely as ameans to manage carbon emissions from coal-based power production (Zwaanand Gerlagh 2009, Friedmann 2007) resulting in carbon credits based onavoidance of carbon emissions. However, no unequivocal means to measure,monitor, assess or to provide or an early warning system for leakagefrom such carbon capture and storage projects is available, though it iswidely acknowledged that such a system is urgently needed (Ha-Duong andLoisel 2009). Thus, it would be highly valuable to have a system ofsystems with means to integrate natural and industrial/anthropogeniccarbon flux resulting in data compatible with carbon based financialinstruments. Such a system does not currently exist although such asystem is needed to advance the capability for measuring, monitoring,verification and accounting carbon credits based on carbon reductiontechnologies such as carbon capture and storage.

Currently, networks of gas collection and analysis are managed bygovernmental entities, such as the National Oceanic AtmosphericAssociation (NOAA) and Commonwealth Scientific and Industrial ResearchOrganization (CSIRO). The sites for which both ¹³C and ¹⁴C analyses areconducted by various groups, such as NOAA and CSIRO, are small, ataround 20 locations representing primarily oceanic sample sites. Forexample, Turnbull et al. (2007) utilize measurements from only twolocations for a study on the variation of ¹⁴CO₂ in North America. Dataresults of Turnbull et al. (2007) clearly indicate that a vast increasein the data rate of ¹⁴CO₂ is required for high resolution of carbonemissions. The current program of ¹⁴CO₂ sampling by governmentalagencies is thus not sufficient to provide data that can be used tosupport carbon trading and related markets.

Based on data to date, changes in relative abundances of differentisotopologues on the order of 10⁻⁴ or 0.1 per mil have significance inanalysis of sources and sinks (Keeling 1958), particularly for ¹³C.Moreover, in demanding field studies to adequately determineatmosphere-ecosystem exchange of CO₂ in forests, for example, eddycovariance measurements are required (Saleska 2006; Gulden et al.,1996). In this case a very fast response time for analysis of 13CO₂ onthe order of 1 Hertz or less for analysis times with a precision of aminimum of 0.1 per mil ¹³C ratios are required to capture the fullbiological response over discrete time periods and over diurnal periodsof forests to a variety of factors (Saleska et al., 2006). Thus, a fastresponse time, stability and high precision would also be useful incases where forest exchanges of CO₂ are needed. Currently, as discussedpreviously, while recognized as important and valuable, forests are notincluded as offsets under the Kyoto Protocol due to the difficulty ofmeasuring and quantifying forest flux of carbon stored (e.g., Saleska etal., 2006) in the soil and the above ground biomass. Thus, a system ofsystems that is capable of measuring and quantifying forest carbon fluxon a variety of time scales including very fast sampling periods tocapture the fine scale and diurnal variations in forest biologicalresponse would be important to providing a basis for forest carboncredits under the current Kyoto Protocol and other conventions ortreaties allowing inclusion of the forests of the world in carbonmanaged and carbon reduced paradigms.

Moreover, a reliable and verified accounting of forest flux could alsobe used to establish carbon trading prices and volumes in any number ofvoluntary exchanges such as the Gold Standard and others (Hamilton etal., 2008). The addition of monitoring the ¹⁴C flux of forests has notbeen used in carbon trading platforms or served as the basis of carbonfinancial instruments. The addition of ¹⁴C data in measuring,monitoring, verifying and accounting for carbon storage in forests willprovide an additional criteria to constrain carbon flux determinationsand indicate the extent to which forests take up fossil fuel emissions,thereby valuing forests to mitigate such emissions. Thus, while theimportance and scientific understanding of forest carbon processes arewell established and the need for widespread measuring, monitoring,verification and accounting is widely recognized as critical, no suchsystem of systems has been devised or is currently operating.

Data Limited Models for Carbon Emissions Determination

Currently, models for deriving reliable carbon flux are data limitedbecause, as explained above, widespread systems for measuring,monitoring, verification and accounting for carbon isotope ratios arenot available. Typically, atmospheric CO₂ concentration measurementsobtained from ground stations and satellites are integrated withatmospheric circulation models to infer emissions from the land surfacein a process referred to as tracer-transport inversion. This approach isinherently difficult using only CO₂ concentration data due to the highlevel of natural variation in CO₂ due to ecosystem carbon exchange,seasonality, and complex atmospheric circulation.

However, the isotopic composition of carbon emissions either as fossilfuel derived carbon or resulting from biogenic carbon flux can provideunique data representing a given area (e.g. spatial extent such assquare meters, miles, etc.) and a given time period (e.g. temporaldefinition, daily, monthly, seasonal) of analysis. An ensemble ofmulti-isotopic analyzers distributed over a defined area is an importantcomponent of a system of systems that can provide data for unknownsources of CO₂ even with large natural variations of CO₂ concentrations.Concentration data for total CO₂, ¹³CO₂ and ¹⁴CO₂ directly measured inone or more locations are required but not sufficient alone to calculatecarbon flux data that can be used for carbon trading and for carbonfinancial instruments. Typically, models are used in conjunction withdata to interpret features of interest and, in the case of carbontrading, final results provided as metric tons carbon or metric ton ofcarbon equivalents for a defined geographic area, are required. It iswidely recognized that due to the paucity of data for the isotopiccomposition of atmospheric CO₂ carbon budgets over a range of scales arelimited in spatial and temporal resolution (Pacala et al., 2009; Tans etal., 1996).

However, even though it is widely acknowledged that models are severelylimited due to a paucity of isotopic data, a system of systems toprovide increased data rate for ¹³C and ¹⁴C is not available. Currentmodel efforts utilizing the sparse data for ¹³C and ¹⁴C readilyillustrate the limitations of models as needed for the rigorous andreliable accounting for carbon trading (e.g., Kosovic 2008). In additionthe placement of ¹³C and ¹⁴C isotopic analyzers is dependent on avariety of factors including topography, vegetation cover, seasonalityand wind patterns. Without a system of systems that can be deployed inthe field under a variety of placement locations, strategic placement ofisotopic sensors cannot be evaluated. Based on current data, theplacement of isotopic analyzers should be such that additions of fossiland biogenic carbon to a given location or area of monitoring is withinthe detection limits of the analyzers. Thus, high precision, rapid andsimultaneous analyses for ¹³C and ¹⁴C to promote effective measuring,monitoring, verification and accounting cannot be accomplished without asystem of systems which is not currently available. Moreover, it is alsoclear that in order to measure, monitor, verify and account foranthropogenic carbon emissions, sampling stations and ensembles ofanalyzers should be placed in areas of large emissions, such as cities,specific industries and broad areas that might represent carbonemissions otherwise thought to be sequestered such as in the case ofcarbon capture and storage. The existing monitoring networks sponsoredby a variety of governmental agencies are specifically not designed tomeasure carbon emissions from large local and regional sources. Suchgovernment sponsored sampling locations were chosen to detect naturalsources and sinks over large scales such as across oceans andcontinents. Such data are not, therefore, suited to measure, monitor,verify and account for anthropogenic carbon emissions or serve as abasis for carbon credits (e.g., Vaughn et al., 2010).

Isotopic Mass Balance and Equivalency Relationships for Biogenic andFossil Derived CO₂ in the Atmosphere

The determination of one or both of the carbon isotopologues at a givenlocation does not in itself provide sufficient data for determination ofthe total mass of carbon for either ¹³C or ¹⁴C that is ultimatelydesired for carbon trading based on metric tons of carbon. Simplenumerical treatments for limited isotopic data are well represented inthe scientific literature but are not adequate to meet the needs ofcarbon trading. Measurements of rare forms of carbon dioxide areprovided relative to isotopic standards and are expressed as deltaratios according to the following formulas:

For ¹³C isotope ratios: δ¹³C (per mil ‰)=[(^(13/12) C sample/^(13/12) Cstandard)−1]×1000

For ¹⁴C isotope ratios: d14C (per mil ‰)=[¹⁴/¹² C sample/¹⁴/¹² Cstandard)−1]×1000.

However, it is widely acknowledged that due to limited spatial andtemporal data for ¹³C and ¹⁴C for a given location or area, such dataare too sparse to support the needs of carbon trading. In most simpleterms, and as familiar with isotopic mass balance equations by thoseskilled in the art (e.g., Levin et al., 2003), one can estimate regionalfossil fuel CO₂ from measured ¹⁴CO₂ and CO₂ concentration using thefollowing mass balance equations:

CO_(2 measured)═CO_(2 biological)+CO_(2 background)+CO_(2 fossil fuel);and,

CO_(2 measured) (δ ¹⁴C_(measured)+1000‰)=CO_(2 background) (δ¹⁴C_(background)+100‰)+CO_(2 biological) (δ¹⁴C_(biological)+1000‰)+CO_(2 fossil fuel) (δ ¹⁴C+1000‰)

In the above equations, CO₂ measured, is the observed CO₂ concentrationfrom a given location or locations, CO₂ background, represents theconcentration of CO₂ at a reference clean air site (e.g., Globalview2006), CO₂ biological, is the regional biogenic component, and CO₂fossil fuel, is the fossil fuel component for the region of themeasurements. The ¹⁴C/¹²C ratios of these components in the deltanotation are, respectively, delta ¹⁴C measured, delta ¹⁴C biological anddelta ¹⁴C fossil fuel. Delta ¹⁴C is the per mil (‰) deviation from the¹⁴C/¹²C ratio from the National Bureau of Standards (NBS) oxalic acidstandard activity corrected for decay (Stuiver and Polach 1977).

Thus, solving for CO₂ fossil fuel yields the following equation:

CO₂ fossil fuel=[CO_(2 background)(δ¹⁴C_(background)−δ¹⁴C_(biological))−CO_(2 measured) (δ¹⁴C_(measured)−δ¹⁴C_(biological))]δ ¹⁴C_(biological)+1000‰.

A similar set of equations can be constructed for ¹³C ratios ofatmospheric CO₂. In addition a number of models are known to thoseskilled in the art to calculate total carbon values from isotopic dataover time and space, but are too data-limited to provide sufficientinformation to be used for carbon trading, as emphasized by Kosovic etal. (2008). Levin & Rodenbeck (2008) present data for ¹⁴C measured bycollection of air samples representing two locations and spanning aperiod from 1985 to 2006. Using an atmospheric transport model TM3(Heimann 1996) Levin and Rodenbeck (2008) conclude that stronginter-annual variations in ¹⁴C must be accounted for relative tochanging trends in fossil fuel source emissions, and that high precision¹⁴C data from a large observational network is desired. Such anobservational network is disclosed herein. Thus, despite a recognizedneed within the model community for vastly increased data for ¹⁴C thatis required to meet the measuring, monitoring, verification andaccounting needs of the Kyoto Protocol, no such system of systems is inoperation.

Likewise, the scientific literature presents many cases of isolatedmeasurement of ¹³C and ¹⁴C and related models to elucidate carbon fluxin a variety of settings such as forests (e.g., Urbanski et al. 2008;Uchida 2008), discrete locations (e.g., Lai et al. 2006; Graven et al.2009) and for oceanic carbon flux (Randerson et al., 2002). However,these studies typically do not result in carbon data for purposes ofcarbon trading. Additionally, the many model approaches utilized do notoffer a comparative basis of the results for geographically andwidespread discrete locations.

The difficulty in providing a large number of isotopic analyzerssituated in grids relevant to the area of interest and that producecomparative data with reference to well known standards is acknowledgedby the absence of such systems. The difficulties are many, such as theinherent difficulty in field ready isotopic instrumentation, continuousdata collection, landscape scale coverage by numerous instruments and ameans to ensure comparative data from all instruments wherever they maybe situated, and the like. Thus, such a system of systems accomplishingthe aforementioned tasks would be highly desirable and needed to addressthe requirements presented by widespread carbon trading.

The difficulty in providing isotopic data for large scale models is evenmore demanding than providing data for limited models as describedabove. The end result required to yield carbon values in terms of metrictons carbon must be rigorously determined for a defined area and for adefined period of time representing a three dimensional framework. Inessence, features of the atmosphere such as mixing and meteorologicalconditions must be matched to real time fluxes of the ¹³C and ¹⁴Cisotopic species. For example, Peters et al. (2007) describe a largescale, three dimensional model approach for North America that combinesdaily CO₂ concentration from a set of 28,000 carbon mole fractionobservations from diverse locations with an atmospheric transport modeldriven by meteorological fields and a CO₂ transport model (Peters etal., 2007). The model results are widely recognized as being highlyvaluable but does not meet the needs of carbon trading because, asdiscussed earlier, the CO₂ concentration data does not reveal theunderlying carbon sources (e.g., fossil fuel CO₂ emissions versusbiogenic CO₂ emissions). Indeed, this approach starkly illustrates thedisparity between CO₂ concentration data and isotopic data.

As described earlier, approximately 100 locations are currently sampledfor carbon isotopes with locations for the collection and analysis for¹⁴C being represented by about 25 locations. In addition, in most allcases the ¹³C and ¹⁴C analyses are not performed in real time, are notcontinuous, nor are they typically simultaneously determined on the sameair sample introducing potential errors. Additional examples ofappropriate models include the MM5 model (Grell et al., 1995) useful foratmospheric mesoscale meteorological applications, the LSM1 model (Bonan1996) representing a large scale land surface model, the TAPMatmospheric model (Hurely et al, 2005) representing areas of hundreds ofmeters, and the bLs model (Flesch 2004) also utilized for atmosphericmapping over hundreds of meters. An example of the extent to which ¹³Cand ¹⁴C analyses would be needed to determine fossil fuel emissions isprovided by the work of Riley et al. (2008). In this work given theabsence of ¹⁴C analyses obtained by direct measurements of air samples,Riley et al. (2008) utilized plant samples as proxies for atmospheric¹⁴C representing plants from 128 sites throughout CA. The plant sampleswere analyzed for ¹⁴C content using accelerator mass spectrometry. Rileyet al. (2008) conclude from their measurements that flows of fossil fuelCO₂ from large sources in the State of California are predominantly tothe south instead of the east as commonly assumed. Thus, this workprovides clear indication of the importance of ¹⁴CO₂ measurements forstate wide emissions regulations such as defined by California AB32 (ARB2010) legislation and for development of larger regional emissionspatterns. The use of plant samples by Riley et al. (2008) in lieu ofanalysis of whole air samples emphasizes the need for a vast increase of¹⁴CO₂ measurements. However, as described above despite the recognizedneed for isotopic data of sufficient spatial and temporal coverage thatcould be used in a variety of models over many scales, the collection ofisotopic data enabled by a system of systems to fulfill the model needsis not available.

Thus, a system of systems that could be placed in many locations (e.g.,thousands) and for which simultaneous ¹³C and ¹⁴C measurements could bemade continuously offering linkage with 3D models incorporatingmeteorological and landscape scale ecosystem data would be highlydesirable and could provide a vastly improved understanding of carbonbudgets for fossil fuel related emissions and biogenic carbon emissionsand cycling at many scales ranging from point sources, to cities tostates and to regions. Although the importance of such a system ofsystems is clearly recognized and long sought after, no such systemexists due the inherent difficulties in the existing methods formeasurement of isotope ratios and their use in frameworks suitable toenable carbon trading.

Laser Based Analysis of Carbon Isotopologues

Isotope ratios of CO₂ and other greenhouse gases of interest includingN₂O and CH₄ are traditionally measured by magnetic sector isotope ratiomass spectrometers (IRMS). These instruments employ a mechanical dualinlet system, require high vacuum and careful sample preparation ofdiscrete, pure gases and offer precision on the order of 0.05 per milfor ¹³C of CO₂ (Vaughn et al., 2010). However, magnetic sector devicesare not suitable for in situ continuous flow analyses required for fieldmeasurements. The natural abundance of ¹³C in the biosphere isapproximately 1.1% relative to total carbon. In addition, themeasurement of ¹⁴C composition typically requires a radiometric analysisor an Accelerator Mass Spectrometer (AMS) facility that also relies onisotope specific ion counting as well as high vacuum and low samplethroughput (Boaretto et al., 2002). The measurement of ¹⁴C istechnically more demanding as one skilled in the art recognizes due itslow natural abundance at approximately 1×10⁻¹² relative to total CO₂. Inboth cases, traditional analytical schemes for ¹³C and ¹⁴C are difficultdue to the ease with which isotopic fractionation can occur during gasmanipulation from sample collection to sample analysis (Werner & Brand2001) obscuring the original isotopic signal. Isotopic fractionation canoccur due to changes in temperature, pressure, water vapor, instrumentperformance, instrument standards, and other internal factors that areoften specific to individual laboratories.

The need for high precision for both ¹³C and ¹⁴C ratios is easilyunderstood when considering that the global growth rate and seasonalisotopic variations are small in well mixed air consisting ofapproximately 1.9 ppm CO₂ and 0.025 per mil ¹³/¹²C (Vaughn et al.,2010). High precision ¹³C isotope ratios can be made with a precision of+−0.01 per mil (1 std deviation) (Vaughn 2010) using traditional isotoperatio mass spectrometers. For ¹⁴C, a change of approximately 2 (e.g.,2.8) per mil represents approximately 1 ppm change in fossil fuel CO₂(e.g., Riley et al., 2008). Thus, the current precision of approximately2 per mil in ¹⁴C measurements is sufficient to identify a 1 ppm changein fossil fuel CO₂. However, no analyzer is available that continuouslyand simultaneously analyzes ¹³C and ¹⁴C with the precision needed andthat is field deployable. In addition, samples utilized for ¹³C and ¹⁴Canalyses are consumed during analysis and cannot be re-analyzed a numberof times, a shortcoming that limits precision obtainable through repeatanalyses of the same sample and/or longer analysis times (Werner andBrand 2001). Thus, traditional high precision methods of analysis for¹³C and ¹⁴C are not suited for field deployment and rapid analysis froman instrumentation perspective nor for coordinated use of large numbersof analyzers to support carbon pricing, trading and carbon management.Such a system is recognized as being highly valuable and long soughtafter and is not available.

One approach to avoid many of the shortcomings of isotope ratio massspectrometry is the use of laser absorption spectroscopy. Laserabsorption spectroscopy may also be used to quantify isotopologues of anumber of gases including CO₂. Laser absorption spectroscopy was firstapplied to CO₂ in the early 1990's (Becker et al., 1992; Murnick andPeer 1994). Laser based approaches are possible due to specificexcitation of vibrational-rotational transitions of gas molecules usingfinely tuned lasers. Thus, laser excitation of the rare species of CO₂,for example, can be used to probe and quantify the concentration of suchmolecules in a gas stream. FIG. 3 illustrates the frequency andwavelength domain of the relevant CO₂ isotopologues and thecorresponding lasing transitions (Freed 1990). The arrows indicateselected lasing transitions for detection of the isotopologues of ¹⁴CO₂101 and ¹³CO₂ 102 and for the most abundant form of CO₂ (¹²CO₂) 103. Theuse of laser based analyzers offers the option of employing sealedreference gas cells with standard gases that can be prepared in largequantities from air and additions of CO₂ based on high precisiongravimetric gas preparation (e.g., Amico di Meane et al., 2009). Suchsealed reference gas cells can be deployed in a large number ofmulti-isotopic analyzers and thus provide a foundation for comparisonsbetween instruments as well as provide a high degree of stability andenable one key element of a system of systems. However, no such use ofsealed reference gas cells is in use in a large number of strategicallyplaced multi-isotopic analyzers. As can be appreciated by one skilled inthe art of fabrication of sealed CO₂ lasers (e.g., LTG Lasers Ontario,Canada) such sealed reference gas cells are achievable in large numbers.

To date, a number of laser based devices have demonstrated successfulmeasurement of the most common isotopologue of CO₂, namely ¹³C¹⁶O¹⁶O.Pulsed quantum cascade lasers have been reported to measure ¹³CO₂ with aprecision of less than 0.1‰ with a 20 s averaging time (Tuzson et al.,2008) under ideal laboratory conditions. Cavity ring down laserspectroscopy disclosed by U.S. Pat. No. 7,154,595, published Dec. 26,2006, and available commercially, reports precision of 0.3‰ using thePicarro G1101-I model employing a 10 s averaging time. Aerodyne ResearchInc., Billerica, Mass., offers a pulsed quantum cascade laser offering aprecision of 0.2 per mil using a 1 s averaging time. A laser basedsystem utilizing a non-optical measurement approach, the opto-galvanicmethod, is disclosed in U.S. Pat. No. 5,394,236, published Feb. 28,1995; U.S. Pat. No. 5,783,445, published Jul. 21, 1998; U.S. Pat. No.5,818,580, published Oct. 6, 1998; U.S. Pat. No. 5,864,398, publishedJan. 26, 1999, reporting ¹³C precision of 0.1‰ with a 10 s averagingtime. Thus, to one skilled in the art of laser spectroscopy,determination of ¹³CO₂ ratios is achievable with commercial devices, butare not currently capable of meeting the required precision (e.g., <0.1per mil) and are not specific for ¹⁴CO₂.

Moreover, the systems described above, with the exception of theoptogalvanic methods referenced, rely on an optical detection method ofthe excited ¹³C isotopologue that is limited in accuracy and precisionof such approaches. Specifically, the laser based devices for ¹³Creferenced above cannot detect ¹⁴C due to limitations in detection giventhat the natural abundance of ¹⁴C is 1×10⁻¹⁰% in the atmosphere. The ¹³Csystems described above do not teach a method or approach to detect ¹⁴Cnor to combine a ¹⁴C system with a ¹²C and ¹³C system. A multi-isotopicanalyzer that simultaneously measures ¹³C, ¹⁴C and ¹²C is of obviousimportance but is not currently available. In addition, such ¹³C laserbased systems that are available now are not deployed with a widelyknown and distributed ¹³C sealed gas reference cell and are not linkedwithin a system of systems and thus such analyzers operated alone cannotbe used to determine carbon fluxes to support carbon trading and carbonfinancial instruments.

To date, there are no commercially available laser-based systems for thedetermination of ¹⁴C in ambient air under continuous flow conditions.Only analyses of discrete air samples ranging from 500 cc to 3 liters(Vaughn et al., 2010) collected in evacuated flasks are utilized withconventional instrumentation. (e.g., Tans et al. 1996). However, asystem disclosed in U.S. Pat. No. 7,616,305, published Nov. 10, 2009,and described in Murnick et al., 2008, offers a ¹⁴C measurementtechnology. The teachings of U.S. Pat. No. 7,616,305 and of Murnick etal., (2009) are incorporated herein by reference and provide the basisfor a feasible ¹⁴C laboratory system. The system of Murnick disclosed inU.S. Pat. No. 7,616,305 represents a two cell system comprised of aspecific laser for ¹⁴CO₂ and ¹²CO₂ but does not teach the analysis of¹⁴C of CO₂ in air but rather the analysis of ¹⁴C in pure CO₂. Aprecision of approximately 1% (10 per mil) is reported. Murnick et al.,(2009) does not teach use of calibration curves for small concentrationsof ¹⁴CO₂ in air nor for a standardization with global referencematerials, all of which would require specialized protocols and methodsthat are not obvious to the experimenter based on Murnick et al., 2008due to complicated behavior of ¹⁴CO₂ and corresponding laser signal withvarying concentration of CO₂. The difficulty in measuring ¹⁴CO₂ can bereadily appreciated given that its natural abundance is approximately1×10⁻¹⁰% of all carbon in the atmosphere. Note that a three cell systemcomprised of ¹²CO₂, ¹³CO₂ and ¹⁴CO₂ lasers integrated in one system hasnot been described nor has the analysis of ¹⁴CO₂ in typical air samplesbeen devised, a requirement for the use of said analyzers for analysisof atmospheric composition related to carbon and biogenic emissions.

In cases where both isotopolgoues (¹³C, ¹⁴C) are determined themeasurement of a sample does not ensure that the data obtained can beused for determination of tradable carbon credits. The determination ofcarbon credits according to biogenic or fossil fuel origin requires anumber of analyzers with routine, repeatable and stable calibration,inter-calibration and global reference systems supported by instrumenthardware, software and data analysis and synthesis. Thus, an instrumentalone capable of measuring one or both isotopologues is not sufficientto reliably provide tradable carbon data. A system of systems approachas described herein is necessary to provide a spatial and temporalframework to collect, analyze, verify and transform carbon flux datainto metric tons of CO₂ of fossil or biogenic origins over specifiedareas and over specific time periods. In addition, no method ofstandardizing reference material that could be used routinely for ¹³Cand ¹⁴C laser based devices regardless of detection system is available.Thus, key components of a system of systems approach to support carbontrading are not available.

Calibration, Inter-Calibration and Global Standardization of Rare Formsof Carbon

Typically, as described earlier, isotopologues of carbon are made bydiscrete measurements obtained by capturing air in an evacuated flaskfrom a variety of locations and analyzed in a small number oflaboratories at widespread locations. Such laboratories maintaininternal standards and shared sets of standards for both isotopologues(¹³C and ¹⁴C) that in principal allow inter-comparisons andcomparability of data from diverse locations. Such inter-comparisons areneeded to construct temporal and spatial trends in isotopologues,however, differences in analytical procedures and preparation ofstandards in individual laboratories can introduce isotopic variation inaccuracy and precision that may obfuscate trends in ¹³C and ¹⁴C ofatmospheric CO₂ and require complicated corrections to data sets (e.g.,Masarie et al., 2001; Werner and Brand 2001; Rozanski 1991; Vaughn etal., 2010). The conventional system of ¹³C standards program currentlycould not support active trading of carbon due to the limited number ofdata and locations. Additionally, errors from each laboratory resultingfrom processing and analysis of the standards according to individuallaboratory practices and according to type of analyzer propagate errorsthroughout the analyses and databases that result from such analyzers.The analysis of ¹³C ratios by IRMS can be influenced by the presence of¹⁷O resulting in a potential shift of 0.03 per mil, and by the presenceof N₂O resulting in a shift of approximately 0.22 per mil (Vaughn etal., 2010). Inter-comparisons for ¹³C data across laboratories has shownvariance up to 10 times larger than the target precisions (Allison etal., 2002, 2003). Differences may be due to gas handling related topurification of CO₂, gas handling related to the analysis of CO₂ and/orto specific operation of a variety of isotope ratio mass spectrometers.Thus, standards that are used internally or those that are shared do notprovide a rigorous cross instrument comparison, a requirement if datafrom one or more instruments located in a variety of locations isneeded. Thus a system of systems that offers instantaneous measurementof ¹³C by a number of widely located analyzers and that are directly andinstantaneously comparable to shared standards would be highly desirablein monitoring, verifying and accounting for variations in ¹³C. Howeverdespite the long term goal of such a network of high precision andcomparable ¹³C and the importance of such a network no such system ofsystems is available. Such a system of systems would be needed tomeasure, monitor, verify and account for biogenic carbon asdistinguished from fossil fuel carbon for the purposes of carbon tradingas related to biogenic carbon flux (e.g., forest carbon sequestration)and for such data requirements for the incorporation of ¹³C data inappropriate models of ecosystems and of meteorological models needed tocalculate carbon mass as a function of time and space.

The case for ¹⁴C standards and inter-calibration are more demanding assmaller samples and more complex instrumentation are required as ¹⁴Cabundance is vastly smaller than that for ¹³C as described above (e.g.,1.1% ¹³C vs. 10⁻¹⁰% ¹⁴C). Samples as small as 0.5 mg total carbon areanalyzed in large complex Accelerator Mass Spectrometers andrequirements for standards of varying ¹⁴C composition are difficult tomaintain free of ¹⁴C contamination (Stork et al., 1997). Due to thedifficulty and expense in analyzing ¹⁴CO₂ and maintaining an AMSfacility a small number of such AMS facilities are available for highprecision analyses (e.g., Boaretto et al., 2002). In cases wherestandards are required that span 0% ¹⁴C, as is the case for fossil fuelCO₂ to increasing fractions of modern ¹⁴C the technical demand inhandling gases properly to ensure that no fractionation takes place isvery high and to-date has not been introduced into a system of systemsas described herein. Isotopic differences can also be related tofractionation during sample concentration (e.g., cryogenic isolation ofCO₂), gas manipulation, and conversion to graphite and analysis (Wernerand Brand 2001). An instrumental method that allows for analysis of ¹⁴Cof both the unknown and a standard reference gas that does not involvesample concentration and manipulation as described above for AMSmeasurements and that is readily referenced by a large number of relatedinstruments would be highly desirable and of obvious importance, but isnot currently available. Thus, as is the case for ¹³C, an instrumentalone that is capable of measuring ¹⁴C composition of an air sample isnot sufficient to support carbon trading and carbon financialinstruments. In addition to the difficulty of analyzing ¹⁴C samplesusing the AMS method large numbers of samples are generally prohibitivedue to the high cost per sample ranging from $400 to $600 per sample. A¹⁴C continuous field analyzer would offer thousands of measurements fora considerably lower cost and in a fraction of the time required for AMSanalyses.

The historical data for ¹³C and ¹⁴C standardization, all provided bystationary instruments at widespread locations show clear and persistentproblems in maintaining world-wide networks of comparable standards, inpart due to the expense and expertise required for analysis of the rareforms of carbon Thus, employing such a network based on traditionalisotopic analysis and the intrinsic errors in these systems for both ¹³Cand ¹⁴C for the purposes of carbon trading have not and cannot beassembled due to the high costs, limitations of the instrument networks,instrumentation and the methods used to analyze and maintain standardsthat can be globally compared. Thus, despite the recognized need andvalue of such a system, no such system of systems currently exists tosupport carbon trading and related carbon financial instruments.

As noted above, to date, no experimental or commercial system currentlyexists that combines systems for measuring and monitoring both ¹³C and¹⁴C in one instrument. Specifically, WO99/42814 does not address asystems of systems incorporating multiple analyzers linked by sharedstandards and global reference standards that are then used to computecarbon in terms of tradable units such as metric tons C for bothbiogenic and fossil carbon fluxes. It is further noted that the art of¹⁴C analyses using laser based methods were not described in sufficientdetail to allow one skilled in the art to build such analyzer. The lowconcentration of ¹⁴CO₂ in the atmosphere being 10-10% of total CO₂ hasnot been accounted for in WO 99/42814 with respect to methods to analyzesuch small quantities being a factor of 10⁻⁹ in natural abundance versus¹³C. WO 99/42814 makes reference to U.S. Pat. No. 5,394,236. However,such reference relates to a laser-based device for determination of ¹³Cand is not applicable to ¹⁴C determinations. ¹³C is present at about1.1% in total CO₂ offering readily available options for its analysis.Thus, WO 99/42814 did not have possession of said ¹⁴C analyzer. Further,such ¹³C and ¹⁴C analyzers were not employed in a system of systemsutilizing integrated components that result in carbon tradable units. WO99/42814 primarily teaches the combined analysis of ¹³C and ¹⁴C but doesnot extend beyond the analysis stage. As we describe below ¹³C and ¹⁴Cisotope ratios alone are not sufficient to produce carbon credits fortrading on carbon financial platforms.

Importantly, despite the long felt need, it has been realized thatimplementation of the system described in WO 99/42814 as an actual orcommercial system has been especially difficult as different criteriaarises based on the different applications. For example, teachings of WO99/42814 could not be carried out to measure and monitor carbon flux inocean water as carbon gases had to be stripped from the water, which wasneither described nor suggested. Other applications, such as measuringand monitoring carbon in a forest, agricultural area, soil, and thelike, prove difficult as proper data sampling rate coupled with theproper spatial density of measurement is neither described nor suggestand was not readily recognizable.

Carbon Trading Carbon Trading and Carbon Financial Instruments

Currently, carbon based financial instruments are centered on standardunits for carbon as expressed in metric tons (1.1 short ton) ofCO₂-equivalence (mtCO₂e) (IPCC 2008). However, direct measurements ofthe flux of CO₂ expressed as metric tons are lacking In addition, datafor carbon expressed in metric tons are used to establish carbon offsetsin cases where an offset is generated by the reduction, avoidance orsequestration of greenhouse gas (GHG) emissions achieved by a givenproject. However, direct measurements confirming the actual number ofmtCO₂e emissions produced, or confirming by direct measurement theabsence of emissions in cases of reduced or avoided emissions (in thecase of offsets) are lacking. Estimation of CO₂ emissions is used basedon fuel consumption (and/or reduction from prior levels) at a givenlocation or number of locations including a trading group, such as theEuropean Union Emission Trading Scheme (IPCC 2008). Thus, in the absenceof actual measurements, uncertainty is unknown, representing a fatalproblem in the method of quantification of emissions; small source termerrors propagate and magnify downstream process errors such as pricingof carbon based financial instruments and their derivatives. Uncertaintyreduction can only be achieved by high precision measurements across thelandscape of a region or trading area. Currently, there are no suchregional measurement stations employing multi-isotopic devices for therare forms of carbon to be used in the reduction of uncertainty forcarbon based financial instruments. Thus, it would be highly desirableto employ a broad-based multi-geographic system to measure, report andverify carbon emissions (reductions of emissions) that are comparableacross a trading landscape as large as continents for CO₂ and relatedgreenhouse gases. No such system currently is available to reduceuncertainty in carbon-based instruments.

Likewise, existing carbon exchanges, domestic and international, (e.g.,Chicago Climate Exchange (CCX), www.chicagoclimatex.com; EuropeanEmission Trading System (EUETS), www.ec.eurpa.ed)) do not specifybiogenic or fossil forms of carbon data nor direct measurement that arerequired to support carbon-based financial instruments. The CCX issuestradable Carbon Financial Instrument® (CFI®) contracts to owners oraggregators of eligible projects on the basis of estimatedsequestration, destruction or reduction of GHG emissions. All CCXoffsets are issued on a retrospective basis, with the CFI vintageapplying to the program year in which the GHG reduction took place.Projects must undergo third party verification by a CCX approvedverifier. All verification reports are then inspected for completenessby the Financial Industry Regulatory Authority (FINRA, formerly NASD).Offset projects can be registered by Members, Offset Providers andOffset Aggregators. Entities that have significant GHG emissions areeligible to submit offset project proposals only if they have committedto reduce their own emissions to the CCX Emission Reduction Schedule asMembersCCX has developed standardized rules for issuing CFI contractsfor the following types of projects including methane (agricultural,coal mine, landfill), soil carbon (agricultural, rangeland management),forestry, renewable energy and ozone depleting substance destruction.However, in all cases of carbon emissions/reduction, direct measurementsof the emissions offsets for CO₂ are not employed by the CCX or thirdparty verifiers either as total CO₂ or as the relevant isotopologues ofCO₂ (e.g., ¹³C, ¹⁴C) (CCX, www.ccx.com). The lack of measurementintroduces uncertainty and errors of unknown magnitude, a complicationthat can affect carbon pricing, market dynamics and facilitate fraud.

In the case of soil carbon, CCX criteria are provided as standardoffsets for CO₂ on a per acre basis depending on geographic location.For example, soil carbon offsets are issued on a per acre per year basis(CCX, www.ccx.com). The offset issuance rate depends on the region inwhich the practice is being undertaken. For instance, enrolled producersin Illinois may be issued offsets at a rate of 0.6 metric tons of CO₂per acre per year and producers in central Kansas may be issued offsetsat a rate of 0.4 metric tons CO₂ per acre per year. The different offsetissuance rates are taken to reflect the differing carbon sequestrationcapacity of the soils in any given location. Thus, estimates are placedon carbon sequestration for land areas without actual measurement. Toone skilled in the art of carbon soil and ecosystem dynamics, such amethod is flawed and likely propagates substantial errors in estimationof carbon sequestered. Data from instrumented towers located in forests,for example, clearly show wide variations in net carbon flux from yearto year and strongly suggest that simple alogorithms for hypotheticalforests and other land-based ecosystems are likely to be in error (e.g.,Urbankski et al., 2007). Likewise, all listed offset projects by the CCXdo not specify measuring, monitoring, reporting or verification methodsin detail and do not require estimation of errors of assessments. Thus,the CCX as with all major carbon exchanges does not set the standardsfor actual and direct measuring, monitoring, reporting and verification.These tasks are left to third party verifiers that use a wide range ofestimation programs. Stable isotopes are not used for verificationpurposes and, further, are not linked to a set of international globalstandards that allows for comparison of carbon flux from differentregions of a state, a group of states of from different continents.Thus, current carbon markets are not based on instrumental measurement,standards and global reference systems that are required to capturedata, reference signals and spatial and temporal coverage overdesignated trading regions, but rather estimation with unknownuncertainty. Thus a system of system that corrected the deficiencieslisted above would be highly desirable, but is not available.

Existing Use of ¹⁴C in Standard ASTM Methods

¹⁴C ratios on solids and gases produced by combustion of solids usingtraditional scintillation counting methods and Accelerator MassSpectrometry (AMS) are used in the context of ASTM D-6866 (ASTM 2008) toestablish bio-based content of fuels and flue gases that are producedwith varying amounts of bio-based source materials, primarily plantbiomass (see FIG. 2, biodiesel blends). The gas stream analysis is basedon discrete samples of gas collected in evacuated flasks and are notused to assess wide scale fossil fuel contributions but to verify pointsource emissions for bio-based content relative to specifications. The %biogenic based material and resulting CO₂ are designated as carbonneutral and thus does not count towards the carbon emissions cap for aspecific industry (Hämäläinen et al. 2007). Specifically, data for ¹³Cand ¹⁴C based on current methodology does not incorporate continuousanalysis or linked standards for ¹³C and ¹⁴C measured together such thatmeasurements are intercomparable wherever they may be made and such thatmeasurements can uniformly and accurately be used to establish carbontrading units and to establish the basis for carbon financialinstruments. Thus, the measurement of ¹⁴C using multi-isotopic analyzersas disclosed herein provides a fundamental advancement over existingsingle sample analysis for ¹⁴C as well as expands the value ofmulti-isotopic analysis as described previously. The use of the ASTMD-6866 provides a fundamental methodology that will be vastly expandedby the teachings disclosed herein.

Thus, based on the descriptions provided in the previous sections it isclear that instrumentation, standards and references and systems levelreporting and referencing are not available that specify an equivalencyrelationship between concentrations of isotopologues in the atmosphereand monetization of emissions or sinks for the purposes of carbontrading and the reduction in uncertainty of errors in the units ofcarbon traded. Accordingly, a need remains for a means of distinguishingbetween and quantifying carbon budget components, and a means tointer-compare data across time and spatial scales as well as referenceall measurements within a global reference system required for planetarycarbon management and carbon trading. Such a system of systems, however,is not currently available based on the efforts of those skilled in theart of isotopic analysis.

An additional approach to quantify carbon emissions is based on spaceborne measurements of CO₂ using a variety of spectrometers. Satellitecampaigns such as the Orbital Carbon Observatory (OCO), Greenhouse gasObserving Satellite (GOSAT) and the Atmospheric Infrared Sounder (AIRS)provide diverse measurements of CO₂ and other greenhouse gasmeasurements (Pacala et al., 2009). Each satellite has specific remotesensing capabilities and offer promise to measure fossil fuel emissions.However, satellite approaches cover a small sensor path and area as ittravels in space over the Earth. While satellites are highly desirablefor greenhouse gas measuring and monitoring, such data cannot support adetailed inventory of emissions to be used for carbon trading accordingto the requirements for any given location, area and over a given periodof time since the satellite is moving according to the pathwaydesignated rather than manipulation of pathways to specific sites withstationary data collection. Moreover, the cost of satellite systems arehigh and may return a limited number of years of observations requiringlaunching of new satellites (Pacala et al., 2009). However, acombination of satellite sensor data and ground based observations, suchas those from an array of multi-isotopic analyzers withinter-calibration, reference protocols and appropriate models to ensurethat data from fossil CO₂ emissions are credible would be highlydesirable.

An arrangement in which a satellite with CO₂ sensors passes over anarray or a ensemble of multi-isotopic analyzers allowing crosscomparison of ground with satellite data would be highly desirable andof great value in providing additional third party verification formeasurement of CO₂ emissions. Further, a ground based and satelliteintegrated measuring program may also offer an additional masterreference sealed cell signal to directly compare ground based standardgases in sealed reference cells to a set of such cells carried as partof the satellite payload. Thus, one can ensure that an inter-comparisonbetween satellite on-board carbon sensors and ground based carbonisotopic data are valid. Thus, while integrated ground based andsatellite based programs would be highly valuable and recognized as suchby those skilled in the art of space based CO₂ measurement systems, nosuch integrated systems are available.

Various embodiments of a system of systems described herein addressthese difficulties, and provides a new approach that is singular in itsapplication compared to existing technology.

Certain embodiments provide a system allowing for collectingconcentration and isotopic data, such as for atmospheric CO₂isotopologues including ¹³C, ¹⁴C and ¹²C, from a diverse spatial arrayof devices that report data in real-time based on shared calibrationroutines, shared primary and master reference data and routines and thatanalyze data, combining such data with diverse model approaches toreveal carbon mass for given spatial and temporal project areas. Suchderived carbon mass are rendered as metric tons carbon or equivalentsand used by financial institutions for carbon trading and/or to guidepolicy makers. The reporting of data for carbon trading can occur withhigh frequency enabling real-time financial transactions or with lowerfrequency and time period averages useful for discontinuous carbonfinancial transactions. In certain embodiments, a system disclosedherein allows for simultaneous measurement of multi-isotopic species inambient air, such that source(sink) terms are identifiable, quantifiableand recognized as isotopic equivalents to standard CO₂ emissions andoffset units, such as a metric ton of carbon or a metric ton of carbonequivalents. The system of systems approach disclosed herein makes useof sealed reference cells being identical and deployed in all analyzersin a given area providing for comparable carbon data across all analyzerlocations and time periods of data collection. The importance of thiscapability can be appreciated by considering the difficulty inconstructing carbon budgets without information about the componentsources as is evident in current carbon trading mechanisms andapproaches that are based on estimation rather than actual measurement.

System of Systems

Certain embodiments provide a system of systems for simultaneouslymaintaining and reporting data on multiple isotopologues. FIG. 4illustrates a block diagram of the instrument package as a component ofa system of systems according to an embodiment. The apparatus includesan all weather housing 517, an optics module 500, housing one or morelasers for each isotopologue including but not limited to a ¹³C lasermodule 501, a ¹²C laser module 502, and a ¹⁴C laser module 503, acooling module 504, a sample module 505, containing one or more sealedreference cells 507 for each isotopologue and one or more sample cells508, a standard reference gas module 509, a power module 510, a cpu andtelemetry module 515 with telemetry antenna 516, a samplepre-conditioning module 511 containing one or more water removal units512 and one or more particulate removal units 513, and a module servingas a platform for additional sensors 514 as desired to complementisotopic data.

FIG. 5 illustrates a diagram summarizing exemplary system of systemsanalysis locations of the instrument package shown in FIG. 4. Typicallocations as described are examples and do not preclude other samplelocations. The multi-isotopic analyzer 600 can be employed in a varietyof locations including on the ocean surface to extract dissolved oceanicgases 601, such as CO₂, dissolved in seawater or other bodies of waterthat may be extracted in situ and admitted to the apparatus, within acity for city-scale measuring and monitoring of industrial (coal,natural gas) and automobile CO₂ emissions 602, sampling within the soilatmosphere or on the surface of a soil 606 at vulnerable locations onthe planet such as high latitude soils with high carbon content wherelarge scale sampling of the soil atmosphere could be used as an “earlywarning” system for soil carbon release in response to surface warmingof high latitudes, within natural forested areas of the world 605 wherelarge amounts of carbon are tied up in soil, woody and leaf biomassrepresenting either very large potential sinks or sources of CO₂ relatedto global warming and forest management, within agricultural settings604 to measure carbon flux of agricultural fields that may also serve assource or sink depending on agricultural methods, watering regime andapplication of fertilizers, and within flue gas from power plant stacksand related CO₂ sequestration projects 603 where leakage of fossil fuelsfrom storage locations is key to effective management and development ofstorage processes.

Referring to FIG. 6, in summary a typical system utilizes a pump 30 todraw the sample gas mixture into the system 2. The sample is next passedthrough a detector to measure the overall concentration of the desiredspecies in question 4. The overall concentration of the desired speciescan be measured via an infrared gas analyzer 4 or in any other fashionappropriate to the configuration and species being measured.

The sample is then optionally passed through a preconditioner 7. Thepreconditioner performs one or more of the following operations:particle removal to clean the sample of particulate, component removalto remove one or more component gases from the sample (i.e., componentsthat may interfere with later processing and detection), concentrationof the desired species, and addition of a carrier to facilitateprocessing. In particularly harsh environments, particle filtration maybe applied at an earlier position in the sample path.

Still referring to FIG. 6, the system passes the sample to one or moreisotope ratio analyzers 24. The analyzer detects the concentration of apredetermined isotope of the desired species. The analyzer may be anyconventional isotope analyzer. Some embodiments employ a small andaccurate laser based unit. For instance, a laser tuned to emit radiationat a wavelength appropriate for the predetermined isotope of the desiredspecies can be used to excite the isotope species into an excited state(see FIG. 3). Simultaneously, the laser excites a known standard of theisotope species. Any suitable type of detector, such as a photodiodedetector or an optogalvanic detector can be used to measure the level ofexcitation of both the sample and the standard and thus detect theconcentration of the isotope. The isotope ratio is calculated bycomparing the isotopic species concentration to the total speciesconcentration measured earlier in the path.

In some embodiments, one or more detectors, preconditioners and isotopeanalyzers are combined, allowing the simultaneous measurement ofmultiple isotope ratios within the sample. They may be configured in avariety of system architectures, with some units operated serially andothers operated in parallel. Referring to FIG. 7 one type ofpreconditioner module 36 may be employed to scrub oxygen from the inletairstream 34 such as available from Teledyne Instruments, model TAI O₂scrubber, containing copper oxide and aluminum oxide rendering an oxygenfree gas 38. Referring to FIG. 8 a gas selective membrane 46 such asthat sold by the name of Nafion can be used to remove water vapor froman inlet gas stream 40 that can subsequently be mixed with carrier gas50 and exiting as gas 56 for analysis. Referring to FIG. 9, a cryogenictrap 82 may be used to concentrate CO₂ in some embodiments taking inletgas 64, mixing as needed with carrier gas 74 and then flowing to trap 82where liquid nitrogen is introduced to the trap with gas flow operatedby a 4 port 2-position flow switching valve 76. Subsequent to trapoperation concentrated gas is directed to the gas outlet 84 foranalysis. Referring to FIG. 10, the cryogenic trap is composed ofstainless steel tubing 94 and is heated after trapping with a resistancewire heater 106. The trap is positioned in a dewar 112 to receive liquidnitrogen for the freezing cycle of the trap operation. Referring to FIG.11, a stainless steel bellows 83 is used to decrease the concentrationof inlet sample gas 64 in cases where the concentration is too high foreffective and accurate analysis as measured by a gas concentrationanalyzer 4 (FIG. 6). The inlet sample is admitted to the bellows in aclosed position or compressed position and valves 78 and 80 are closed.Subsequently, the bellows is expanded and carrier gas 74 is admittedallowing the target concentration to be obtained by dilution asdetermined by gas analyzer 4. Subsequently the gas is allowed to flow tothe isotope ratio analyzer 24 via a capillary flow or other means.

In some embodiments, here referring to FIG. 6, the system is controlledby a microprocessor-based data acquisition and control unit 8, such as apersonal computer. The data acquisition and control unit controls theoperation of each portion of the system, collects measurements, performsdata processing and data summary, stores the data and transmits thedata. The data acquisition and control unit may also be connected toexternal sensors so as to measure and monitor conditions external to thesystem (e.g., weather conditions such as temperature, wind direction,wind speed, pressure and humidity, locational information such latitudeand longitude via a global positioning system, and for water basedunits, water temperature and salinity) and internal to the system (e.g.,power condition, temperature, system functionality, etc.) All of theinformation may be transmitted via a radio transmitter to a central basestation that can collect the data, monitor system operations and monitorexternal conditions. The base station may optionally transmit newprograms into the system when the system is configured with a receiverconnected to the computer. Typical systems for wireless communications,well known to those skilled in art, and remote operation of instrumentsinclude the Supervisory Control and Data Acquisition (SCADA) availablefrom, for example, Omega Engineering, Inc. (www.omega.com) among manyother commercially available communication and control architectures.

Finally, the data are employed at spatial and temporal scales and linkedwith suitable models of the atmosphere and biosphere and/or coupledmodels of same providing model imposed volumes to integrate carbonfluxes over temporal and spatial scales needed to monetize carbon in thecontext of carbon trading and exchanges. The end result is a uniqueisotope characterized carbon emission unit based on standards andreferences in which both biogenic and fossil fuel components ofatmospheric CO₂ can be quantified and thus monetized on suitablegreenhouse gas and/or carbon trading exchanges.

In certain embodiments, the system is designed to be modular, portableand self contained. The system can utilize conventional line power butcan also utilize batteries. If batteries are utilized, the system canalso charge the batteries via a solar cell array, thus allowing remoteoperation. In some embodiments, the system is contained in a weatherproof housing that also provides the platform for external sensors,radio antennae and/or solar cell arrays.

Detailed Embodiments

Illustrative non-limiting embodiments will now be described to providean overall understanding of the disclosed system of systems and relatedmethods. One or more examples of the illustrative embodiments are shownin the drawings. In certain embodiments, a system of systems is referredto as the Global Monitor Platform (GMP) representing a uniquecombination of isotopic instruments, sensors, standards, globalreferences and data telemetry in a field deployable housing suitable forhoused and remote operation. The GMP provides the capability to decipherpartial and global greenhouse fluxes and thus provides a unique approachto manage greenhouse emissions of the planet to assist in reducing theconsequences of global warming. In certain embodiments, any availabledevice(s) for the determination of ¹²C, ¹³C and ¹⁴C composition of CO₂in ambient air are combined in a modular form factor with samplehandling and sample conditioning features as described below. Inaddition, a system of systems may employ any analyzer for concentrationand isotopic composition of any gas.

Exemplary embodiments of a method and system of systems are showndiagrammatically in FIGS. 6 through 35. FIGS. 6 through 14 showembodiments of the analyzer employed as one component of the system ofsystems but with differing analytical components and operationalfeatures. FIGS. 15 to 22 describe embodiments of additional operatingand methodological components of the system of systems includinginstrumentation arrays, calibration and inter-calibration ofinstruments, global references, system architecture and datatransmission and methods employing models to produce market readyaggregated data in the context of partial carbon budgets. Referring toFIG. 22 a partial carbon budget is a subset of the global carbon budgetreflecting local, regional and otherwise geographically limited areas.

The method and system of systems employ from 1 to any number of devicesneeded in spatial arrays of the devices placed across the areas ofapplication referred to in FIG. 5 and according to point, local,national and/or state boundaries and greenhouse gas treaties as shown inFIGS. 23 through 35. The apparatus, in one embodiment featuringruggedization and full remote operation, may be placed virtuallyanywhere on land and on any body of water, on and or under any surfaceand in any airspace of the planet Earth. The method and system ofsystems provides for the placement of devices according to the need forspatial resolution, preferably from 1 device per square mile to 1 deviceper 4×5 degrees latitude/longitude or according to the specificenvironmental and geological conditions at a given site and asdetermined by initial operation and testing of the systems of systemsfor optimal function to produce carbon tradable results. Further,certain embodiments include sampling inlets representing air from thesoil column, soil and/or vegetation surface(s) and within a verticalprofile extending from above the surface to any height supported by anystructure including but not limited to tree trunks/limbs, buildings,towers, and structure with height as well as including samples obtainedfrom aircraft, balloons or other means.

Some embodiments employ a microprocessor-based data acquisition andcontrol unit (shown as item 8 in FIG. 6) capable of acquiring andstoring the data generated by the infrared gas analyzer (IRGA) (shown asitem 4 in FIG. 6) and the isotope ratio analyzer (shown as item 24 FIG.6).

Calibration and Instrument Inter-Comparison and Primary ReferenceProtocols

As described previously, the analysis of isotopic composition results indata that are expressed as ratios, most simply stated as the data for anunknown against a known reference standard. The ratio approach andappropriate standards for both stable and radiogenic isotopes are welldeveloped but not used in the context of requirements for carbontrading. However, when employing a number of isotopic analyzers, the keyissue of individual and grouped calibrations and inter-comparisons andlinkage to global references becomes a difficult and time intensiveeffort as described previously and recognized as a material obstacle tothe implementation of a system of systems to support carbon trading andcarbon management.

However, even with the advent of laser based continuous flow analyzerssuch as those described herein (e.g., gas filled isotopic lasers and/orquantum cascade lasers), the issue of single and multiple instrumentcalibration and inter-comparisons is required to obtain reliable andverifiable data for carbon emissions that can be used to support carbontrading across multiple geographic locations. In the present case, inwhich isotopic data are to be used to create integrated flux data forcarbon, based on dispersed analyzers at diverse locations, thecalibration, inter-calibration issue is a requirement if significantreduction in uncertainty for carbon trading is to be realized.

Assumptions in calibration and inter-comparisons include the following:

-   1) that the assigned δ¹³C of the sealed-cell standard is correct,    particularly when changing standard cells;-   2) that the response of the analyzer(s) does not substantially vary    one from another over time and in space;-   3) that the respective samples for a given analyzer or group of    analyzers over time and space are processed to a standard level of    purity and pre-conditioning; and-   4) that the response of the system is not dependent on differences    in the source of air with respect to isotopic value, sample size or    flow rate and pressure.-   5) That performance of individual instruments is monitored and    compared to all other instruments in an ensemble of instruments and    that comparisons with primary references, consisting of additional    reference cells within the analyzer and or external cells, can be    used to correct performance issues such as baseline drift or    verification of signals above background. The use of sealed cells to    contain reference gases and which can be compared instantaneously is    an important feature of the system of systems by providing for very    high precision and very high stability over short and long    operational periods of use.

An advantage of the non-IRMS approach using essentially continuous flowambient air with minimal gas handling is that differences amongstanalyzers and most gas handling issues are reduced or eliminated. Beyondthis improvement, another feature of certain system of systems disclosedherein is the use of a variety of sealed standard reference cells withknown isotopic composition as shown in FIG. 12. Such sealed referencecells are shown in FIG. 13 (806, 807, 809) as placed in a three cellinstrument. In certain embodiments, the sealed reference cell consistsof a single glass cylinder (e.g., quartz) approximately 6 cm in lengthand 0.5 cm in outside diameter with permanently sealed zinc selenide(ZnSe) end caps to allow the laser light, unchanged, to pass through thecylinder. The glass cylinder reference cells contain the same standardor reference gas for all analyzers. In certain embodiments, a largenumber of sealed reference cells are filled from the same source ofstandard air and sealed off with a glass torch or other means topermanently seal the cylinder (FIG. 12). The sealed cells may be filledwith a large equilibrated volume of air according to protocols readilyknown to those skilled in the art of CO₂ laser fabrication, such as LTGLaser, Ontario, Calif., and to those skilled in the art of standard gaspreparation. The sealed cell embodiment described herein FIG. 12 andemployed in FIG. 13 is unique in its employment with three isotopicsystems (¹²C, ¹³C, ¹⁴C) and effectively reduces the difficulty ofdifferences within standard gas preparations employed by differentlaboratories as described previously and also would greatly reduce noiseand instrument drift.

The sealed reference cell gas can then be analyzed by a number oflaboratories resulting in highly calibrated standard cells. Referring toFIG. 12 showing a schematic of sealed reference cells consisting ofanalyzer instrument reference cells, external primary or globalreference cells and satellite born 609 reference cells for ¹³CO₂ 606,¹⁴CO₂ 608 and a mixture of ¹³CO₂ and ¹⁴CO₂ 607. Sealed referencestandards for ¹⁴CO₂ comprising a set of global standards for which otherlaboratories have obtained data could range from 100% fraction modern¹⁴CO₂ 600 to 0.5% fraction modern 601 to 0% fraction modern 602. Sealedreference cells for ¹³CO₂ may consist of ¹³C isotope ratios of −25 permil 603, −5.00 per mil 604, and +10 per mil 605. Each primary or globalreference sealed cell is made such that all sealed cells for aparticular isotopic composition are identical (610, 611, 612), thusensuring comparison between analyzers in an ensemble and acrossensembles wherever they may be located. Such multiple reference cellscould be arranged in a linear array or in any placement that allowsmirrors to effectively direct the laser beam through all cells offeringinstantaneous baseline and reference calibration. The use of a sealedreference cell or cells allows the calculation and precision of isotoperatios in a manner analogous to that used with dual inlet IRMSinstruments. However, sealed reference cells as described according tocertain embodiments herein are used within a framework of calibrationand inter-comparison routines applied as appropriate over temporal andspatial scales of interest.

Referring to FIG. 13 a schematic is shown employing three laser cells,¹²C 800, ¹³C 801 and ¹⁴C 802. The combination of the three lasersrequires a balanced approach to detection and optimization of each laseraccording to laser power input and output, stability and modulation. Thethree cell system is one example of an embodiment for all three speciesof carbon, however the system of systems could be deployed with anyisotopic analyzer for any isotopic species. Details of the operation ofthe three cell system (FIG. 13) are provided below.

Referring to FIG. 14 a schematic is shown for a typical operationalroutine that is encoded into software that is controlled either manuallyor by remote communication. After a sample is introduced to the system ameasurement is made to determine concentration of total CO₂ and pressureor, alternatively, initial data for each of the isotopes ¹³C and ¹⁴C areacquired and entered into the data control software. In the case whereeither the total concentration of CO₂ or the concentration of theisotopic species (¹³C, ¹⁴C) is either too large or too small thesoftware control will direct operations to either increase of decreasethe respective analytes as provided in FIGS. 9, 10 and 11. Once samplesize is considered optimal for measurement a calibration curve maybeimplemented and/or comparison with an external sealed standard may beperformed. Additional details on the use of standardization as describedin FIG. 14 are provided below.

Hardware Architecture for the System of Systems

Referring to FIG. 15 a schematic is provided showing the basic hardwarecomponents consisting of a base instrument 100, a base instrument withsealed reference cell and telemetry capability 102, an array ofanalyzers 103 as in 102, and an array of analyzers in a given locationto measure, monitor, verify and account for carbon emissions 104, inpart effected by instantaneous communication between all analyzers toensure comparability of data. An additional external reference cellcomprising, for example, a primary reference standard may also beincorporated in the array of analyzers to provide an additional means ofensuring analyzer function and comparability of data from all analyzers.

Referring to FIG. 16, an array of analyzers in a given location is shownwith communication between such analyzers 105, which communicates alldata via telemetry or other wireless means 106 to a receiver, such as asatellite 107, the data then being transmitted to a central data stationor data center for analysis 108.

Referring to FIG. 17 a schematic is provided showing threegeographically distinct arrays of analyzers 900, in communication withan external reference sealed cell 901 instrument that allowsinstantaneous comparison and correction to baseline and calibration datavia wireless means 904 for each instrument in the distinct arrays thatmay then be compared with a primary reference 902 that is linked to wellknown international standards for ¹³C and ¹⁴C such as the Vienna Peedeebelemnite (VPDB) standard for carbon 13 ratios (Coplen et al., 2006) andthe National Bureau of Standards oxalic acid (e.g., NBS OxII) for ¹⁴C(Scott et al., 2004). In this embodiment both external reference 901 andprimary standard sealed cells 902 are based within the region to serveeach ensemble. Data are transmitted to data centers to be integratedwith models and used, for example, in one embodiment to support livetrading on greenhouse gas exchanges 906. In another embodiment referencestandards as sealed cells can be housed in a satellite 908 enabled tocompare reference values for ensembles of instruments as the satellitepasses over the geographic region where the land-based ensembles areplaced. Still referring to FIG. 17 passage of a satellite specificallyequipped with greenhouse gas sensing capability 908 over a region withan ensemble of analyzers may also enable direct comparisons of data forland based and satellite sensed greenhouse gas concentrations 907. Instill another embodiment referring to FIG. 17, such data asreceived/transmitted by a satellite for the purposes of ensuringverification of land based analyzers or for the purposes of sensinggreenhouse gas concentrations at the surface, such data may beinstantaneously received and transmitted to support live carbon exchangetrading activity 906 across the planet with all analyzers assured to becomparable and thus monetized in a way that accommodates all currencyflows/exchanges in the same manner as occurs for stock trading acrosscountries and currencies.

Referring to FIG. 18 a schematic is shown in which a data station 109employs software and/or models of any kind that calculates the metrictons of carbon or carbon equivalents for any ensemble of analyzers orgroups of analyzers 110 and 111 across spatial locations and accordingto specified time periods and providing such data to carbon exchanges112, 113 located anywhere trading may be appropriate.

FIG. 19 shows a summary of the main component processes of the system ofsystems for a given geographic area 401, a given time period 402, withinstruments 400 and data from samples measured by analyzers 406, groupsor ensembles of analyzers 400 and data ensembles 406, shared calibrationand inter-calibration protocols 403, global reference protocols 404, andexternal satellite based reference standards 405. All data aretransmitted via wireless or other means of telemetry 407 to data centersthat manage and incorporate the data 408 in one or more models 409 thatultimately are converted to metric tons of biogenic or fossil fuelderived carbon 410. Such units can be registered as credits according tothe rules of a given trading system 411 for sale on an appropriategreenhouse gas trading exchanges, platforms 412.

FIG. 20, panel A, illustrates hypothetical isotope data for ¹³C/¹²C and¹⁴C/¹²C ratios resulting from four instruments in different locationscovering five points in time. The data for the four instruments, denotedby symbols (squares, circles, cross-hatched circles and triangles) areshown in Panel A with solid lines 801 connecting data of similar trendand dotted lines connecting data recognized as outliers 802 and 803. Afeature of the software control protocols according to certainembodiments is to recognize outlier data as it is produced in eachinstrument and recognized by routine calibration curves, primarystandards and external standards (e.g., FIG. 14). Thus, in Panel A, theoutliers above and below the trend line (802 and 803) would beeliminated from the corresponding data stream and instrument primarydata record, although retained in an appropriate file. In someembodiments, each of the instruments (804, 805, 806, 807) may also bereferenced to an external primary reference cell 809 as shown in FIG.14, or may be compared with satellite space based measurementsrepresenting an additional method to cross check data results in realtime and providing a global reference data point. Referring to Panel B,it can be seen further that when such data quality and assuranceprograms are applied to each instrument 804, 805, 806 and 807 within anarray, a software program can be devised to query each instrumentagainst any other instrument 808 (represented by cross arrows betweeneach pair of devices) verifying normal function and otherwiseeliminating outliers or other conditions during which data are eithernot collected or a malfunction is registered. Such controls areessential to ensure comparability for analyzers that are located farfrom each other and in different environments (Panel C). Thus, accordingto certain embodiments, for defined intervals over time and space alloutlier data for all instruments in an array are eliminated from theprimary data set, thus producing a network or data fabric that isquality assured. Non-conforming data may be set to trigger an alarmsignifying that the instrument is not functioning properly. Suchprotocols for arrays of instruments are well known to one skilled in theart of instrument controls and software control of such devicesaccording to set protocols. For example, the National InstrumentCompany, Austin, Tex. (www.ni.com) offers Lab View (e.g., Model 8.6), awell known instrument control software package, that allows custom dataacquisition, manipulation and interactive control of instruments toaccomplish complex routines such as those described above.

This protocol, which can be run automatically in real time usingadvanced wireless control protocols as described below, represents aninter-calibration routine that promotes successful performance of asystem of systems disclosed herein. Note that in Panel C, the locationof the four instruments is such that any combination of data from thelocations may be employed to generate aggregated data and resultssuitable for carbon trading. The discrete locational data representingone or more locations may be used to reduce or expand the spatialfootprint or to track rapid changes in a single location depending onother factors including environmental conditions. The inter-calibrationroutine may be applied to any number of devices located in arrays inmany disparate locations around the world and disparate trading networkssuch as the EU ETS and RGGI carbon trading platforms as referencedpreviously. Such a network or fabric of data can then be integrated withappropriate models to further aggregate and interpolate data to providecumulative carbon fluxes over defined spatial and temporal domains.Thus, the system of systems, according to certain embodiments, offersself regulating calibration and inter-calibration routines to ensuredata comparability in a way that has not been implemented to date forthe rare forms of carbon as disclosed herein.

System Architecture for Data Communication and Transmission Using SCADA

The term SCADA stands for Supervisory Control And Data Acquisition. Suchsystems are readily available commercially from vendors such as BentekSystems, Inc., Alberta, Canada (www.scadalink.com). A SCADA system is acommon process automation system which is used to gather data fromsensors and instruments located at remote sites and to transmit anddisplay this data at a central site for either control or monitoringpurposes. In the certain embodiments, referring to FIG. 21, a SCADAsystem is used to control and monitor isotopic data resulting from theisotopic analyzers 901 as disclosed herein. The collected data isusually viewed on one or more master SCADA Host computers 902 located atthe central or master site with options for intermediate host computers903 such as regional areas that may be employing widely separatednetworks of isotopic monitors. A real world SCADA system can monitor andcontrol hundreds of thousands of input/output (I/O) points. A typicalSCADA application for a system of systems as described herein would beto monitor devices producing isotopic composition for ¹³C and ¹⁴Cisotope ratios, calibration and data transmission for one or moredevices in a given network and for all networks. The various softwareand hardware features of the individual devices and communication withina network of devices are controlled by employing both analog and digitalsignals.

In at least some embodiments utilizing remote sites and/or disparategroups of sites, another layer of equipment between the remote sensorsand instruments and the central computer is employed. This intermediateequipment exists on the remote side and connects to the sensors andfield instruments. The device sensors will typically have digital oranalog I/O and these signals are not in a form that can be easilycommunicated over long distances. The intermediate equipment is used todigitize then packetize the sensor signals so that they can be digitallytransmitted via an industrial communications protocol over longdistances to the central site. Typical equipment, well known to thoseskilled in the art of SCADA, that handles this function are PLC's(Programmable Logic Controllers) and RTU's (Remote Terminal Units)commonly housed in the same instrument box or RTU 901. In certainembodiments, isotopic analyzers spread across one or more landscapeswill be classified as RTU's 901 equipped with PLC's. The RTU and PLC isequipped with the appropriate SCADA communication device 904. One suchSCADA device, common in the industry and well known to those skilled inthe art of SCADA communications devices is the SCADALink 900-MBRTU/radio modern enabling wide-area, remote, point-multi-point SCADAcommunication systems sold by Bentek Systems, Inc., of Alberta, Canada.These devices employ de facto standard industrial data communicationprotocols such as Modbus, AB-DF1, and DNP3.0 to transmit the sensordata, all well known to those skilled in the art of communicationprotocols. Typical physical interface standards are Bel 202 modem,RS-485 & RS-232, also well known to those skilled in the art ofinterface standards.

Typically a SCADA system consists of four major elements:

-   -   1. Master Terminal Unit (MTU) 902    -   2. Remote Terminal Unit (RTU) 901    -   3. Communication Equipment 904    -   4. SCADA Software

The Master Terminal Unit 902 is usually defined as the master or heartof a SCADA system and is located at the operator's central controlfacility. In the illustrated embodiment the MTU represents the primarycontrol and operations center that monitors, controls, receives andprocesses data that is produced by the isotopic analyzers. The MTUinitiates virtually all communication with remote sites and interfaceswith an operator. Data from remote field devices (¹³C, ¹⁴C, CO₂concentration data, calibration routines, alarm conditions, etc.) issent to the MTU to be processed, stored and/or sent to other systems.For example, in the present case the MTU may send the data to regionalcarbon trading platforms anywhere on the planet.

As discussed earlier, the Remote Terminal Unit 901 is usually defined asa communication satellite or node within the SCADA system and is locatedat the remote site; in this case representing individual isotopicanalyzers across the landscape. The RTU gathers data from each of thefield devices in memory until the MTU 902 initiates a send command suchas a command to transmit isotopic data for a given period of time fromone or more field isotopic analyzers 901 or one or more intermediatedata collection sites 903. In one embodiment, isotopic analyzers may beequipped with microcomputers and programmable logic controllers (PLCs)that can perform functions at the remote site without any direction fromthe MTU and is considered herein as part of the RTU 901. In addition,PLCs can be modular and expandable for the purpose of measuring,monitoring and controlling additional field devices. Thus, in thepresent case, in one embodiment, a regional ensemble of many RTUs 901will be equipped with PLCs to specifically measure and monitorcalibration, inter-calibration and reference routines and may also allowcontrol functions, site condition reports, re-programming capacity andalarm functions for one or more isotopic analyzers. Within the RTU 901is the central processing unit (CPU) that receives a data stream fromthe protocol that the communication equipment uses. The protocol can beopen such as Modbus, Transmission Control Protocol and Internet Protocol(TCP/IP) or a proprietary closed protocol; all aforesaid protocols arewell known to one skilled in the art of data transmission protocols.When the RTU 901 sees its node address embedded in the protocol, data isinterpreted and the CPU directs the specified action to take. Allfunctions, thus, can be carried out from one or more master sitescontrolling any number of isotopic analyzers.

In various embodiments, the way the SCADA system network or topology isset up can vary, but each system relies on uninterrupted, bidirectionalcommunication between the MTU and the RTU. This can be accomplished invarious ways, e.g., private wire lines, buried cable, telephone, radios,modems, microwave dishes, wireless/cellular 905, satellites 906, orother atmospheric means, and many times, systems employ more than onemeans of communicating to the remote site. This may include dial-up ordedicated voice grade telephone lines, DSL (Digital Subscriber Line),Integrated Service Digital Network (ISDN), cable, fiber optics, Wi-Fi,or other broadband services. A system of systems as disclosed herein canmake use of all communication systems covering local, regional andremote sites as is well known to those skilled in the art of SCDAsystems.

A typical SCADA system provides a Human Machine Interface (HMI) 907allowing the operator to visualize functions as the system is operating.Accordingly, in the present disclosure, visualization may include,without limitation, contour surfaces of carbon flux, calibration andinter-calibration routines, or simply carbon flux data in metric tons ofCarbon attributed to either biogenic or industrial sources for a givenarray of devices over a given time period. In certain embodiments, theoperator can also use the HMI to change set points, view criticalcondition alerts and warnings, and analyze, archive or present datatrends. Since the advent of Windows NT, the HMI software can beinstalled on PC hardware as a reliable representation of the real systemat work. Common HMI software packages include Cimplicity (GE-Fanuc),RSView (Rockwell Automation), IFIX (Intellution) and InTouch(Wonderware). Most of these software packages use standard datamanipulation/presentation tools for reporting and archiving data andintegrate well with Microsoft Excel, Access and Word. Web-basedtechnology is also accepted as well. Data collected by the SCADA systemcan be sent to web servers that dynamically generate HTML pages. Thesepages are then sent to a LAN system at the operator's site or publishedto the Internet. In the illustrated embodiment, the data after beingreceived by the MTU 902 will be used to generate carbon flux datacompatible for use in one or more carbon exchange platforms 915.

In summary, referring to FIG. 21, a number of isotopic analyzers areplaced in the field in two separate locations 908, 909, all employing aninstrument architecture supporting a PLC within the RTU 901 instrumenthousing. In one embodiment, each discrete location with an RTU isequipped with a SCADA communicator 904. In another embodiment, RTUs thatare close enough to be wired to each other 910 may employ a single SCADAunit for communications. In still another embodiment, handheld computers911 within a given network may also monitor data by wireless or othermeans. In another embodiment, in which wireless communication isinvolved, a repeater unit 912, available from Bentek Systems, Alberta,Canada, and model SCADALink SMX-900, may be involved to boost the signalfor final transmission to the MTU 902. In yet another embodiment, anintermediate MTU 903 is used to capture data prior to transmission tothe primary MTU 902. In yet another embodiment, a solar powered SCADAcommunications unit 913 may be employed in remote areas with limitedelectrical connectivity, using for example, the Solar SCADA Link,available from Bentek Systems, Alberta, and Canada. Data communicationsmay be effected by wireless transmission 905 or satellite 906 systems.The data are received by the primary MTU 902 and rendered in a varietyof displays, including but not limited to contour surfaces for carbonflux, charts, graphs and three-dimensional visualizations within thehuman machine interface, HMI, 907. Appropriate data products resultingfrom the use of mathematical calculations and models finally yieldcarbon flux data in metric tons, specifying both biogenic andanthropogenic/industrial components as sources or sinks for a givenspatial and temporal domain. Such data are encrypted 914 and transmittedto carbon exchanges 915. Data is automatically stored within a varietyof on-site and off-site databases 916.

Model Aggregation of Spatial and Temporal Isotopic Data

Data for ¹³C and ¹⁴C isotopic compositions along with data for CO₂concentration provide the input for a variety of models, ranging fromdiscrete soil carbon models to agricultural models to those coveringmuch larger scales, from local sites to regions to continents to globalmodels. The interplay between the density of the isotopic measurementsites, local meteorological conditions, time period of the measurementsand the mechanistic basis of the models themselves is considered whenusing models to derive carbon flux data that can be used for tradingpurposes as well as when designing sampling sites and arrays ofmeasuring devices.

According to certain embodiments, models are used to interpolate dataobtained from spatial and temporal arrays of isotopic measuring devicesresulting in integrated flux data, in metric tons of carbon, for thearea and/or process that is being measured. In each case, the carbonflux for a discrete spatial and temporal domain represents a partialcarbon budget in the context of the global carbon budget. Carbontrading, by its nature, consists of partial carbon budgets and must becharacterized with acceptable uncertainty and predictive power. Thus, asystem of systems according to certain embodiments described thus farcomprises the methodologies and associated spatial and temporal domainsto craft a wide variety of partial carbon budgets that can be used tosupport carbon trading and ultimately to support a detailedunderstanding of the global carbon budget itself.

Examples of specific areas and/or processes for which integrated fluxdata would be useful for carbon trading are illustrated in FIGS. 22 to35. In each case, a specific model can be used, for example, based onpublished work, to demonstrate efficacy for the given application.Relevant carbon models include soil models published by Zobitz et al.,2008; forest exchange models published by Urbanski et al., 2007 and Sottet al., 2004; regional exchange models published by Lloyd et al., 2001,Levin et al., 2003 and Lai et al., 2006; agricultural carbon cyclemodels published by West and Marland, 2002; regional fossil fuelemissions models published by Kosovic et al., 2008; ocean carbon cyclemodels published by Matsumoto et al., 2004; geologic carbonsequestration models published by Venteris et al., 2006; and continentalscale models published by Peters et al., 2007. While the aforementionedmodel publications are exemplary, the academic literature contains manymodels in the areas described and others suitable for the treatment ofdata to produce material fluxes, reported in metric tons, which can beused by carbon exchanges as verified carbon units. Each ensemble ofanalyzers may require a specific combination of models to yield requiredresults and thus represents a proprietary model integration function fora variety of embodiments of the system of systems.

An overview of discrete system of systems is illustrated in FIG. 22providing frameworks of varying scales, ranging from global budgets 400to discrete soil budgets 403 in the terrestrial domain 408 or discretemarine carbon budgets 405 in the oceanic domain 407. The double endedarrows signify carbon flux in both directions, positive meaning emittedto the atmosphere and downward or negative flux meaning sequestered. Thedual arrows, solid referring to fossil/industrial carbon and the dashedarrows referring to biogenic, natural carbon, show the final outcome ofthe illustrated system of systems, that is, a dual carbon accounting ofthe primary carbon components in the atmosphere. Referring to FIG. 22,all boxes shown represent interrelated budgets focused on components ofthe carbon cycle, both anthropogenic/industrial 409 and natural 407,408. The common model element for an accurate partial carbon budget isatmospheric transport 406. Atmospheric transport in both the verticaland horizontal planes can rapidly move and mix emissions across largespatial scales over short time periods. Such a rendering of the movementhistory and final dispersion of carbon emissions will be useful at thestate and regional levels to manage and monetize carbon emissions asdiscussed by Riley et al., 2008.

A partial budget, in embodiments of large scale efforts such as regionaland continental scales, involves placing an “invisible box” or controlvolume over the area of monitoring, and tracking movement of all airacross the boundaries and the concentrations of isotopes and carbondioxide as precisely as possible. The use of meteorological data withhigh resolution in time and space can be adapted for model use. Inconjunction with isotopic data from an array of devices, this can beused to calculate large scale fluxes. Such an approach is reported byKosovic, 2008, and is well known to one skilled in the art ofatmospheric transport models. The density of measuring points across thelandscape will vary according to landscape heterogeneity, topography,design criteria and desired resolution and accuracy and is optimallyconfigured according to initial test configurations of the system ofsystems.

One example of a model approach well suited for a system of systems asdisclosed here has been reported by Riley et al., 2008. In this study,analysis of leaf samples for ¹⁴C content and hence of fossil fuelemissions were utilized to estimate atmospheric ¹⁴C again demonstratingthat direct measurement of ¹⁴C in the atmosphere is not feasible withcurrent technology. The study coupled MM5, and LSM1 tracer models toinfer fossil CO₂ emissions and movement in the state of California basedon the ¹⁴C of plant data. The MM5 model based on the work of Grell etal. (1995) comprised a nonhydrostatic, terrain followingsigma-coordinate mesoscale meteorological model typically used inweather forecasting and in studies of atmospheric dynamics, surface andatmosphere coupling, and pollutant dispersion. The model has beenapplied in many studies over a variety of terrains, including areas ofcomplex topography and heterogeneous land-cover. The physics packagesused for the simulations can be found in Riley et al. (2008) and arewell known to those skilled in the art of atmospheric transport models.

The LSM1 model used in the Riley et al. (2008) study was fashioned afterBonan (1996) and is a “big-leaf” land-surface model that simulates CO₂,H₂O, and energy fluxes between ecosystems and the atmosphere. Moduleswere included by Riley et al. (2008) that simulate fluxes of radiation,momentum, sensible heat, and latent heat; belowground energy and waterfluxes, and coupled CO₂ and H₂O exchange between soil, plants, and theatmosphere. Twenty-eight land surface types, comprising varyingfractional covers of thirteen plant types, were simulated in the modelas reported by Riley et al. (2008). Riley reports that the integrationof the two models MM5 and LSM1has been tested and found to accuratelypredict the desired fluxes.

Riley et al. (2008) employed a standard initialization procedure for MM5v3.5, which applies first-guess and boundary condition fieldsinterpolated from the NOAA National Center for Environmental Prediction(NCEP) reanalysis data to the outer computational grid. The model wasrun with a single domain with horizontal resolution of 36 km and 18vertical sigma layers between the surface and 5000 Pa; the time stepused was 108 s, and output was generated every two hours. The two hourlymodel output was used in the analyses that follow by integrating oraveraging over hourly, seasonal, or annual periods. An integrated fluxmap resulting from the work of Riley et al. (2008) is shown in FIG. 22B,as an exemplary and readily available model approach for use with asystem of systems offering integrated flux data over varying temporaland spatial scales. The three dimensional contour of flux was determinedwith a model resolution of 36 square kilometers, duly representative ofone embodiment for an array of isotopic analyzers.

Referring to FIG. 22A, and recognizing that each of the partial budgetsshown can be treated in a manner similar to that reported by Riley etal. (2008), the partial budget 401, is comprised of partial budgets 409,402, and 403, in the simple example used. The system of systemsdisclosed according to certain embodiments herein is the only approachknown to date that allows determination of nested partial budgets thatcan be integrated into larger and larger budgets based on real time,high precision flux data for both biogenic and anthropogenic/industrialemissions. Following on from the previous partial budget example,partial budgets 401 and 408 representing the terrestrial domain andpartial budgets 404, 405 and 407 representing the oceanic domain are inmaterial balance with the GB 400 over a given period of time andultimately representing fully mixed air from all partial budgets. Thus,the simplified global budget and partial budgets illustrated in FIG. 22show that a system of systems as disclosed herein offers a means toquantify carbon flux across varying scales of time and space that arecompatible with requirements for carbon exchanges representing variedand discrete locations and carbon budget dynamics.

Again referring to FIG. 22B, the data sets representing discretemeasurements in time and space can be converted to molar volumes ofcarbon emitted, reduced or sequestered. The model data can be processedto cover the carbon flux from major cities, for example, agriculturalareas, wilderness areas and residential areas, all representing partialbudgets. The entire set of partial budgets, for a given geographicalarea can then be used to assemble a carbon budget, for example, for anentire state. Given that each of the partial budgets can be expressed inmetric tons of carbon either emitted, reduced or sequestered, such datacan be directly used to identify carbon credits for trading (e.g.,carboncredits represent carbon reductions or avoided carbon by sequestration).The process of registering credits with carbon exchanges, such as theChicago Climate Exchange or the European Union Emissions Trading Schemeis well known to those skilled in the art of registering and sellingcarbon credits. The process in summary involves identifying acceptabledomains for carbon trading such as agricultural, landfill gas, forestactivities, etc. A project that meets the domain criteria submits anapplication to the exchange involving a series of documents describingin detail the project, location and method of monitoring. Once approved,the project establishes a baseline condition and then begins theproject. Monitoring is performed based on a system of systems approachas described herein. Time periods of monitoring are reported andsubsequently verified and certified by the exchange, after which thecredits are registered on the exchange and listed for sale.

However, measuring, monitoring and verification methods for carbontrading have been to date poorly developed and lacking a unifiedmethodology. In contrast, according to certain embodiments herein, thedata for the state of California, for example, would consist of:

-   -   ¹⁴C units (metric tons): reduced+sequestered−emitted    -   ¹³C units (metric tons): sequestered—emitted

Thus, for the first time, data for carbon trading can be definedaccording to the fossil and biogenic components, as well as providingdata to track management of carbon fluxes due to policy action. The datacan also reveal the source components in greater detail, and assessecosystem function in some cases, as shown in FIG. 2. Thus, a system ofsystems according to certain embodiments integrates natural and fossilemissions, as well as identifies source components and ecosystemfunction.

A system of systems according to certain embodiments herein offers a newapproach using the dual accounting of both biogenic and fossil carbonfluxes to create meaningful carbon credits that may be priced and valuedbased on scientific data that are directly linked to carbon emissions byhumans and the natural environment we live in.

General Operation of the Analyzer of the System of Systems

In some embodiments of the method and system of systems, measurement ofa species concentration and the isotope ratios of the species (e.g.,carbon dioxide concentration and carbon isotope ratios) of a gasmixture, such as air from any source as shown in FIG. 6, is performed,the appropriate data are written to memory in the device and thentransmitted to a central location as shown in FIGS. 16, 17 and 18. Withreference to FIG. 6, the system operates as follows. The gas sample isinput via gas inlet tube 2 into the system. In further embodiments, theinlet tube 2 may be connected to a combustion chamber to provide agaseous sample of a solid. Such a combustion chamber can be formedutilizing a thermo-electric heating element in a chamber holding thesample or can utilize a conventional combustion chamber used in massspectrometer.

The gas sample is pulled into and through the system via operation ofpump 30. Initially a measurement of the total concentration of thesubject gases is conducted. In an embodiment for measuring carbonisotopes, IRGA 4 provides the total CO₂ concentration of the inputsample without the need for preprocessing or conditioning. In additionalembodiments targeted for harsh environments, a preconditioning unit maybe added to remove moisture, dust etc. This can be accomplished, e.g.,by filter units utilizing selective membranes to remove unwantedconstituents as known in the art or utilizing chemical scrubbers as isknown in the art.

The system then passes the constituent gases to one or more optionalpreconditioning units to remove certain constituent gases and toconcentrate the gas or gases of interest. For instance, in someembodiments for determining the concentration of carbon isotopes,isotope ratio analyzer 24 is capable of providing the carbon isotoperatios, but is subject to interference by the presence of oxygen withinthe sample. Therefore in the previously discussed embodiments (asdepicted in FIGS. 7, 8 and 9), the sample conditioning unit 18 is usedto at least remove oxygen from the sample gas before it enters theisotope ratio analyzer 24. The precision of the measurement provided bythe isotope ratio analyzer 24 can be further improved by increasing theconcentration of the desired species within the sample. In someembodiments directed to CO₂ detection, concentration is increased to 1%or more by volume. In addition, the precision can be improved bysupplying an inert carrier into the sample stream. Again, with referenceto certain CO₂ units, the sample containing 1% CO₂, is mixed with purenitrogen or another inert and non-interfering carrier gas. Therefore,the isotope ratio measurements provided by the isotope ratio analyzer24, representing for example three laser cells of ¹²C, ¹³C and ¹⁴C, canbe improved by a sample conditioning unit 18 by concentrating theparticular specie or species in the subject gas sample and by mixing itor them with a carrier gas.

The input sample is next passed to one or more isotope analyzers todetect the various isotopes of the subject gases in the sample. Theisotope ratio analyzer can utilize any device for measuring the isotopiccomposition of a gas, but in some embodiments the system utilizes a lowmass, low power, compact device. For a system measuring carbon isotopes,one such carbon 13 isotope analyzer is taught in U.S. Pat. No.5,394,236. In additional embodiments, for instance an embodiment fordetecting carbon 14, the system utilizes a coherent light sourceemitting energy to resonate selectively for desired subject gas. Forinstance, measuring isotopic carbon 14 would utilize a ¹⁴CO₂ isotopiclaser for radiating the sample and a known standard reference cellcontaining the subject gas, here carbon 14. The ratio measurements maythus be conducted in a manner as taught in U.S. Pat. No. 5,394,236,whose teachings are herein incorporated by reference. In cases whereboth ¹³C and ¹⁴C are analyzed, both must be normalized to ¹²C, the mostabundant form of carbon. Once the analysis is complete, the sample gasesare evacuated from the system into the environment, typically indirection away from the input area.

Variations of the basic system are available. For instance, an expansionupon the basic system is possible by combining a number of the basicbuilding blocks into a single unit to detect additional species andisotopes. In this case, a number of isotope ratio analyzers 24 areutilized. Each analyzer 24 would detect the presence of an isotopicspecies in the sample. Because the system does not consume the sampleduring detection, it is possible to sequentially arrange a number ofdetectors to receive the sample over time. Each ratio analyzer 24 couldoptionally include a preconditioning unit to condition the sample priorto isotopic measurements. In this series configuration, care is given toensure that preconditioning units do not remove desired subject gasesprior to analysis. An alternative architecture is to utilize a splitterto send a portion of the sample to each analyzer in parallel, thusallowing the ratio analyzers to operate independently. In eitherconfiguration, each analyzer could be operated selectively (i.e., onlymeasure certain isotopic samples at certain times to reduce powerconsumption).

In certain embodiments, the system is designed to operate in remotelocations, and/or to measure and monitor additional external conditions(e.g., temperature, humidity, wind direction, time, general weatherconditions, etc) via conventional sensors mounted externally to thesystem. The complete unit is under the control of data acquisition andcontrol unit 8.

Combined ¹³CO₂ and ¹⁴CO₂ Analyzer

A brief overview of the isotopic species and data rate for CO₂ arepresented in Table 1 below. Definitions and estimates of the data ratefor current technology and for an embodiment of the technology disclosedherein are provided, illustrating lack of isotopic data resulting fromtraditional isotope ratio mass spectrometry (IRMS) technology, and thepromise of a much increased data rate employing an embodiment of thetechnology disclosed herein, the Global Monitor Platform (GMP).

TABLE 1 SPECIES FOR DECONVOLUTION OF FOSSIL AND NATURAL CO₂ SOURCESDEFINITION AND DESIRED SYMBOL USE PRECISION TECHNOLOGY/DATA RATE T theCO₂ volume mixing 0.1 ppm LI-COR/ LI-COR- ratio expressed in ppmcontinuous GMP/continuous and on a WMO mole Infrared gas fraction scaleanalyzer, Li-COR. Inc. δ ¹³C the per mille deviation <0.1‰ IRMS/500 yr⁻¹GMP/500,000 yr⁻¹ of the ¹³C/¹²C ratio (NOAA Flask from the VPDB Samplingprimary standard and Program) on the Vienna-PDB scale (Coplen et al.,1995; Allison et al. 1995). δ ¹⁴C the per mille deviation   <2‰ AMS/500yr⁻¹ GMP/500,000 yr⁻¹ of the ¹⁴C/¹²C ratio (NOAA Flask from thestandardized Sampling value of the pre-bomb Program) atmosphere in 1950(Stuiver and Polach 1977)

The rare forms of carbon dioxide employed herein include ¹³C¹⁶O₂ and¹⁴C¹⁶O₂. The multi-isotopic approach employed here may also be appliedto all of the isotopologues of CO₂ including ¹²C¹⁸O¹⁶O, ¹³C¹⁶O¹⁸O,¹²C¹⁷O₂, ¹²C¹⁸O₂, ¹³C¹⁸O₂, ¹⁴C¹⁸O₂ (Freed 1995, Bradley et al., 1986).Although atmospheric CO₂ is used as an example here, any gas that can begenerated and measured from any source is applicable (FIG. 5), forexample, soil gases, gases generated in closed spaces, experimentalchambers, and experimental apparatus or on other planetary surfaces.Some of these gases may include, but are not limited to: methane,nitrous oxide, molecular oxygen, hydrogen and nitrogen, water vapor andcarbon monoxide.

According to certain embodiments, the GMP analyzer, referring to FIG. 4,is employed, including the following main components: threewavelength-tuned isotopic CO₂ gas lasers 501, 502, 503; RF-powersupplies 510; a CO₂ calibration cell(s) 507; an air sample cell 508;low-pressure, low-flow gas handling hardware 511; diagnostic and controlsensors 514; trap and drying components for sample preparation 511; amulti-channel signal analyzer 515; and a control computer and software515. In the illustrated embodiment, the three wavelength-tuned isotopiclasers consist of ¹³C 501, ¹²C 502 and ¹⁴C 503 lasers. However, anyother wavelength-tuned isotopic laser may be used for any of theisotopomers of CO₂ or for any other relevant greenhouse gas such as N₂Oand CH₄.

The instrument may be packaged as a Class 1 laser system per the Foodand Drug Administration (FDA) Center for Devices and Radiological Health(CDRH) requirements to cover the use of the ¹⁴CO₂ gas used for the ¹⁴CO₂laser even though the amount of radiation contained in the laser cavityis less than background ¹⁴C radiation. The instrument is to include areference methodology, e.g., one or more reference gas cells, to allowdetection ratios to be calibrated and correlated between multiple unitsindependent of their physical location. In certain embodiments, externaland satellite based reference cells and communications capabilities toreport isotopic data and diagnostic information to a central locationare to be incorporated into the integrated product.

In certain embodiments, a GMP analyzer measures the isotopic compositionof CO₂ in the atmosphere based on the interaction of wavelength-specificlaser energy within an ionized plasma volume. Referring to FIG. 13, thisis accomplished in one embodiment utilizing the optogalvanic effect byinducing a change in the impedance of the plasma media through anoptogalvanic effect (OGE). The impedance change, detected as a voltagechange, can be correlated to the specific isotopic concentrationsrelative to the specific wavelengths of the excitation beams. In thecase of the GMP analyzer, ¹²CO₂, ¹³CO₂ and ¹⁴CO₂ gas lasers permit theaccurate detection of ¹²CO₂, ¹³CO₂ and ¹⁴CO₂ isotopic concentrations andtheir ratios when wavelengths are tuned to the appropriate wavelengths.

Again referring to FIG. 13, according to certain embodiments, the basicconfiguration of the GMP unit consists of isotopic lasers, such as for¹²C 800, ¹³C 801 and ¹⁴C 802, mirrors, M1 to M7, a chopper to modulatethe ¹⁴C laser 810, three RF oscillators for excitation and a circuitboard for detection and differential amplifier boards 803, 804, 805contained within the laser units 800, 801 and 802, opto-galvanic (OGE)standard reference cells 806, 807, 809, an OGE flowing gas sample cell808 with 4 ZnSe windows allowing for ¹²C, ¹³C and ¹⁴C laser beams tointeract with sample gases, sample gas drying and handling hardwareconsisting of a mass flow controller 811, a Nafion filter 820, a drynitrogen gas tank or nitrogen generator 832, pressure sensors 813, 814and a dry pump 823 from which the sample exits after analysis either inflow mode or in batch mode, a residual gas analyzer 812, standard gasesfor use in the flow cell 831, 824, a four port mechanical switchingvalve 819, single flow valves 816, 817, 818, oxygen scrubber 821,particulate filter 822, automated switching gas manifold valve 825,sample inlet ports 826, a piezo circuit for beam centering is employedin all three lasers leading to a master piezo circuit controller 827, adata acquisition board (DAQ) 828, a computer module (CPU) 829 and atelemetry system and antenna 830 and a power supply 833.

The three cell system referred to in FIG. 13 provides for the threelaser beams to be suitably misaligned relative to each other to preventback reflections propagating from the secondary laser output opticalelements back into the primary laser cavity. This prevents instabilitiesin the laser outputs. While many embodiments of a system of systemsdisclosed herein are used for the simultaneous measurement of rare formsof carbon, the device may also serve as a platform to host relatedsensors. Small and lightweight sensors such as those for carbonmonoxide, radon, methane, and other trace gases can further refinesource and sink components for regional carbon budgets. Carbon monoxideis a key component of automobile exhaust (e.g., Levin et al., 2008).Methane can be indicative of both natural and anthropogenic sources(e.g., Levin et al., 2008). Radon is often used in conjunction with ¹⁴Canalysis (e.g., Levin et al., 2008). Other devices that may be placed onthe unit include without limitation global positioning system GPS forlocation information, temperature, relative humidity and rain sensors.

Lasers and Optical Elements

In certain embodiments, the laser output energy is at a stablewavelength (line) that is consistent with the isotope of interest basedon the quantum transition energy. Specific output wavelengths are10.51-10.70 μm for ¹²CO₂, 11.06-11.26 μm for ¹³CO₂, and 11.8 μm for¹⁴CO₂ (Freed 1980). Wavelength control of the lasers in the GMP unit isaccomplished, e.g., with closed-loop feedback control of PZT elements (apiezoelectric ceramic material) for each laser (FIG. 13, 827) varyingthe laser cavity length. In one embodiment, the PZT elements arecontrolled with THORLAB's MDT 691 single channel piezoelectric drivers.

In certain embodiments, the laser output of the individual lasers ischopped at discrete frequencies to differentiate the OGE induced changein the output signal through Fourier transform methods. The choppingfrequency of the ¹⁴C and ¹³C lasers is nominally 17 Hz and 25 Hz in oneconfiguration. The laser beams are directed via coated silicon or coppermirrors into the OGE cells. ZnSe is used for the OGE cell windows 806,807, 808 and 809.

Detection Cells and Sample Preparation

In certain embodiments, as shown in FIG. 13, 4 OGE detection cells areused in the isotopic detection system. A sealed cell contains a standardreference isotopic ¹²CO₂ composition 806, a ¹³CO₂ standard referencecell 807, a ¹⁴C standard reference cell 809 and a sample flow cell 808.These cells use pressures of approximately 3.5-4.0 torr. The sample gascell uses a flow rate of approximately 0.4 sccm.

Stable performance of the OGE cells involves humidity control of thegases. For the standard reference cell this is accomplished bycontrolling the gas sealed in the cell. In contrast, the sample gashandling system includes gas drying capabilities 820 (FIG. 13). Thewater vapor content tolerance on the sample gas is less than 1.5%relative humidity in the sample in one embodiment utilizing gas filledisotopic lasers and optogalvanic detection approach. Referring to FIG.13 plasma fields are generated in the gas volumes in the OGE cells seenas a glowing discharge in both the sample 808 and reference cells (806,807, 809),with RF power supplied by the RF driving boards contained inthe lasers 803, 804 and 805 along with data acquisition boards.

Electronics and Control

Off the shelf components, well known to those skilled in the art oflaser operation, can be used in the GMP unit for gas pressure 813, 814(FIG. 13) and flow measurement and control 811 (FIG. 13), PZT elementcontrol for all three lasers 827 (FIG. 13), power supplies, dataacquisition boards 803, 804, 805 (FIG. 13), temperature control, andsoftware and computers 829 (FIG. 13). Features of these components areonly based on satisfying the requirements of the GMP unit for specificapplications.

The integrated laser systems in one embodiment with ¹³C, ¹²C and ¹⁴Clasers will therefore have three isotopic laser beams chopped atdiscrete frequencies propagating through the detection cells. Such anintegrated system, in one embodiment, also accounts for the relativemagnitude of the concentration of the ¹⁴CO₂ isotope in the atmosphereversus the ¹²CO₂ and ¹³CO₂ concentrations. Atmospheric air consists ofapproximately 0.03% CO₂. ¹³CO₂ constitutes approximately 1% of thecomposition within this 0.03%. In contrast, ¹⁴CO₂ constitutesapproximately 1 part in 10¹² within the 0.03%. Today the 1.18×10⁻¹²concentration of 14_(CO) ₂ in the atmosphere is called 1 modern levelconcentration and is the basis for scientific comparison of ¹⁴C levels.The detection of such small quantities of ¹⁴CO₂ requires a much higherOGE signal gain for the ¹⁴CO₂ than the ¹²CO₂ and ¹³CO₂. Thus, two rangesof detection, data analysis and data summary must be accommodated.However, to one skilled in the art of laser systems, this issue can beovercome by appropriate adjustments in laser power, laser cavity lengthand time period of data acquisition for a given sample and can bedetermined by conducting a series of experiments controlling forspecific factors of interest.

One solution to the relative difference in isotope concentration hasbeen accounted for in US Patent Application Publication US 2008/0129994,incorporated herein by reference, showing a configuration of propagatingmultiple passes of the ¹⁴CO₂ laser beam through the OGE cell situatedwithin the standing wave of the ¹⁴CO₂ laser cavity. This designinterpretation has demonstrated detection limits approaching 10⁻¹⁵¹⁴C/¹²C in published reports (Murnick et al., 2008) which are similar toaccelerator mass spectroscopy (AMS).

The noted concentration differences of the isotopologues impact inseveral ways. First, the optical design of the system accommodatessingle pass beam excitation in the sample OGE for the ¹²CO₂, ¹³CO₂ and¹⁴CO₂ detection and standing wave beam propagation for the ¹⁴CO₂detection. One embodiment as shown in FIG. 13 is to have one sample OGEcell for detection of all three carbon species ¹²C, ¹³C and ¹⁴C. This isaccomplished by splitting the ¹²C beam with M4 allowing a ¹²C referencesignal to pass through both the ¹³C and ¹⁴C cells such that the data canbe normalized against ¹²C and reported in the isotope ratio formuladefined earlier. The small detection limits necessitate managing thedetection signal-to-noise ratio including design features applicable toprovide the higher signal fidelity.

An additional feature of this multi-isotopic embodiment is maintaining astable detection signal. Specifically, it has been demonstrated thattemperature fluctuations within the OGE cells, the lasers and thedetection electronics manifest themselves as OGE signals similar toisotopic changes. Drifts in the wavelength of the laser output manifestthemselves in a similar manner. Thus, the accurate temperature controlof the lasers, the OGE cells and the electronics is provided for in theGMP and, while this is achieved in the laboratory, as referenced invarious documents above, with a re-circulating chiller, one embodimentwill feature advanced solid state thermal management as shown inelements 834, 835, 836 (FIG. 13). In summary, a multi-isotopic analyzeraccording to certain embodiments includes a ¹²C, ¹³C and ¹⁴C embodimentas shown in FIG. 13. In such an embodiment certain components of thecombined system may be shared, referring to FIG. 13, including thecomputer and software system 829, data acquisition boards 828, gashandling components including pumps 831, pressure sensors 813, 814, flowcontroller 811, sample dryer 820 and dry tank nitrogen gas or nitrogengenerator 832.

Example Operation of a Carbon 12, 13, 14 Analyzer

As noted previously, isotopic analyzers based on optical detectionsystems have inherent limitations with respect to accuracy and precisionfor ¹³C and have no capability for the analysis of ¹⁴C. One embodimentof the GMP analyzer includes the use of opto-galvanic analyzers for ¹²C,¹³C and ¹⁴C. However, the system of systems approach disclosed hereinmay be employed with any type of suitable analyzer for ¹²C, ¹³C and ¹⁴Cisotopes. The aforementioned non-optical approach, the opto-galvanicapproach, provides sensitivity to measure near 0% modern radiocarbon.This technique achieves specificity to isotopic chemical species via theuse of the optogalvanic effect (”OGE″). The OGE can be measured withhigh signal to noise background ratios, and is proportional to laserpower and is integrated over the discharge volume (Murnick and Peer1994, whose teachings are herein incorporated by reference) and yieldprecision similar to that of the traditional mass spectrometers. Thedischarge is converted into an electrical signal and processed for aspecified period of time, relative to a sealed standard gas chamber,depending on the required precision. Long measurement intervals, inprinciple, will exceed the precision typical of traditional isotoperatio mass spectrometers (i.e., <0.01 per mil). Advantages of OGE can beunderstood from the following equation (Murnick and Peer 1994):

S=nLI(v)Aσ(v)C   (1)

where the electrical response, S, of the system with laser of averageintensity (Wcm⁻²) I and frequency v is incident on a weak electricaldischarge, n is the density of interaction species, L is the length ofthe interaction region, σ defines the laser-species interaction crosssection and C is an optogalvanic proportionality constant. Note that,according to (1) the signal is linear in both density [n] and laserpower [I]. Increases in laser power provide for increased gain offeringenhancement of signals for dilute or very low concentration of isotopesrelative to the majority species. Improvement of signals by varying gasmixtures, gas pressure and discharge power are possible and affect theparameter C. Unlike absorption and fluorescence measurements dependenton optical elements, OGE reduces collection and dispersion optics andlight transducers. Small discharge variations are canceled out bysimultaneous measurement; the use of sealed working reference gases. Asdescribed previously (resulting in long life) promises to reduceinstrument drift, off-sets between batches of standards prepared often(as is the case for traditional mass spectrometry) and differencesbetween laboratories, which can be significant for the current flasksampling programs. Remotely operated units could process samples, e.g.,for as long as one hour intervals throughout the day to achieve highprecision for measurement of atmospheric CO₂ isotope ratios (i.e.,<0.05‰) or, e.g., for as short as 1 second (yielding precision for ¹³Cand ¹⁸O of at least about 0.01 and 0.1‰, respectively) for use in fastanalytical schemes for plant physiological or biological monitoring.Samples can be analyzed in a semi-continuous batch mode or in continuousflow mode; each configuration may employ different hardware, asdescribed in the embodiments previously. In particular, in oneembodiment in the case of CO₂, three isotopic lasers are employed, oneto determine the ¹²C content, one to determine the ¹³C/¹²C ratios and anadditional one to determine the ¹⁴ C/¹²C ratio (Freed, C. 1990 whoseteachings are incorporated by reference).

Example of Specific Operation

The operation of one embodiment of the instrument for this example is asfollows. With reference to FIG. 6, under the control of the dataacquisition and control unit 8, power is applied from power supply unit14 to pump 30. Since the IRGA 4, sample conditioning unit 18, isotoperatio analyzer 24 and the pump 30 are all connected with coupling tubes5, 7, 9 in order to provide a continuous gas flow path, gas present atgas inlet tube 2 is drawn through all of the tubing-coupled componentsand out of vent tube 33. After the gas has passed through the IRGA 4, itpasses through the sample conditioning unit 18 before entering theisotope ratio analyzer 24. As the gas is drawn through the oxygenscrubber 36 (as shown in FIG. 7), which constitutes the sampleconditioning unit 18 in this embodiment, oxygen is removed. Theoxygen-free gas continues to be drawn through coupling tube 7 and intothe isotope ratio analyzer 24. After sufficient gas has been drawnthrough the isotope ratio analyzer 24 to purge out any residual gas froma previous measurement, the data acquisition and control unit 8 stopsthe pump 30. Now that both the IRGA 4 and the isotope ratio analyzer 24have received appropriate aliquots of the gas drawn in from the gasinlet tube 2, the data acquisition and control unit 8 initiates aconcentration measurement of CO₂ by the IRGA 4 and an isotopicmeasurement of CO₂ by the isotope ratio analyzer 24. Measurement datagenerated by the IRGA 4 and isotope ratio analyzer is acquired andstored or transmitted by the data acquisition unit 8. The whole sequenceof events can be repeated either immediately, or after a delay period asdictated by the program loaded into the data acquisition unit 8.

Operation of the embodiment with the sample conditioning unit 18comprising the apparatus shown in FIG. 8 is as follows. Initially,solenoid valve 60 and flow-controlling valve 54 are closed allowing nogas to flow through them. Under the control of the data acquisition andcontrol unit 8 (see FIG. 6), the solenoid valve 60 is opened and poweris applied from power supply unit 14 (see FIG. 6) to pump 30 (see FIG.6). Gas present at gas inlet tube 2 (see FIG. 6) is drawn into andthrough the IRGA 4 (see FIG. 6), through the coupling tube 5 (see FIG.6), through the gas inlet tube 40, through the gas chamber 42 andthrough the solenoid valve 60. The gas continues to be drawn throughcoupling tube 62, coupling tube 29 (see FIG. 6), pump 30 (see FIG. 6)and finally out of the vent tube 33 (see FIG. 6). The gas selectivemembrane 46 provides considerable resistance to the gas flow and so doesnot allow a significant amount of sample gas to pass through it duringthis stage of operation. When enough gas has been drawn through the IRGA4 (see FIG. 6) and the gas chamber 42 to purge any gas remaining fromprevious measurements, the data acquisition and control unit 8 (see FIG.6) closes solenoid valve 60. Since the IRGA 4 (see FIG. 6) has receiveda suitable aliquot of sample gas, the acquisition and control unit 8(see FIG. 6) initiates a CO₂ concentration measurement. The pump 30 (seeFIG. 6) continues to run and establishes vacuum conditions in theisotope ratio analyzer 24 (see FIG. 6), coupling tubes 7, 9, 29 (seeFIG. 6), gas outlet tube 56, and coupling tube tee 48. When the pump 30(see FIG. 6) has run long enough to achieve the desired vacuum in theattached components, the acquisition and control unit 8 (see FIG. 6)stops the pump 30 (see FIG. 6). The CO₂ in the sample gas contained inthe gas chamber 42 now permeates the gas selective membrane 46 due tothe pressure difference across it.

The CO₂ in the sample gas contained in gas chamber 42 is allowed topermeate the gas selective membrane until enough CO₂ has accumulated inthe evacuated components to provide precise isotope ratio measurementwhen mixed with an appropriate amount of carrier gas, e.g., purenitrogen gas. Under the control of the data acquisition and control unit8 (see FIG. 6), the flow-controlling valve 54 is opened enough to allowa charge of pure nitrogen gas to flow from the carrier gas source 50,through coupling tube 52. The nitrogen passes through coupling tube tee48, through gas outlet tube 56, through coupling tube 7 (see FIG. 6) andinto the isotope ratio analyzer 24 (see FIG. 6). Most of the CO₂ whichhad previously permeated the gas selective membrane 46 FIG. 8 is carriedby the nitrogen gas flow into the isotope ratio analyzer 24 (see FIG.6). The flow-controlling valve 54 is closed by the data acquisition andcontrol unit 8 (see FIG. 6) when a suitable charge of gas is present inthe isotope ratio analyzer 24 (see FIG. 6). At this time, the dataacquisition and control unit 8 (see FIG. 6) initiates an isotopemeasurement of the CO₂ in the isotope ratio analyzer 24 (see FIG. 6).Measurement data generated by the IRGA 4 (see FIG. 6) and isotope ratioanalyzer 24 (see FIG. 6) is acquired and stored or transmitted by thedata acquisition unit 8 (see FIG. 6). The whole sequence of events canbe repeated either immediately, or after a delay period as dictated bythe program loaded into the data acquisition unit 8 (see FIG. 6).

Operation of another embodiment with the sample conditioning unit 18comprising the apparatus shown in FIG. 9 is as follows. Initially,solenoid valve 66 and flow-controlling valve 72 are closed allowing nogas to flow through them. Under the control of the data acquisition andcontrol unit 8 (see FIG. 6), the solenoid valve 66 is opened and poweris applied from power supply unit 14 (see FIG. 6) to pump 30 (see FIG.6). The data acquisition and control unit 8 (see FIG. 6) also sets thecryogenic trap 82 into the non-trapping state so that gas can flowfreely through the cryogenic trap.

Next, gas present at gas inlet tube 2 (see FIG. 6) is drawn into andthrough the IRGA 4 (see FIG. 6), through the coupling tube 5, throughthe gas inlet tube 64 and through the solenoid valve 66. The gas is thendrawn through coupling tube tee 68, cryogenic trap 82 and through thegas outlet tube 84. The gas flow then continues through the couplingtube 7 (see FIG. 6), isotope ratio analyzer 24 (see FIG. 6), couplingtube 9 (see FIG. 6), pump 30 (see FIG. 6), and out through the vent tube33 (see FIG. 6). When enough gas has been drawn through the cryogenictrap 82 to purge any gas remaining from a previous measurement, the dataacquisition and control unit 8 (see FIG. 6) sets the cryogenic trap 82into the trapping mode. Gas continues to flow from the gas inlet tube 2(see FIG. 6) all the way through the tubing-coupled components whilecondensable gas components are cryogenically trapped in the cryogenictrap 82. When gas has been flowing for a long enough time to allow anappropriate quantity of CO₂ to accumulate in the cryogenic trap 82, thedata acquisition and control unit 8 (see FIG. 6) closes solenoid valve66 and allows the pump 30 (see FIG. 6) to establish vacuum conditions inthe coupling tube tee 68, cryogenic trap 82, outlet tube 84, couplingtubes 7 and 9 (see FIG. 6) and isotope ratio analyzer 24 (see FIG. 6).The data acquisition and control unit 8 (see FIG. 6) now initiates aconcentration measurement on the aliquot of gas contained within theIRGA 4 (see FIG. 6). When the pump 30 (see FIG. 6) has continued to runfor long enough to achieve its ultimate vacuum in the attachedcomponents, the acquisition and control unit 8 (see FIG. 6) stops thepump 30 (see FIG. 6) and sets the cryogenic trap 82 back to itsnon-trapping state in order to release the trapped gas. As the gas isreleased from the cryogenic trap 82, it expands throughout thecomponents previously under vacuum. When enough time has expired toallow the trapped sample to completely evaporate, the data acquisitionand control unit 8 opens the flow-controlling valve 72 to allow thecarrier gas, preferably pure nitrogen, from the carrier gas source 74 toflow through it. The nitrogen gas flows from the flow-controlling valve72, through coupling tube tee 68, through the cryogenic trap 82, and outthrough the outlet pipe 84. The nitrogen flows through coupling tube 7(see FIG. 6) and into the isotope ratio analyzer 24 (see FIG. 6)carrying most of the previously trapped sample gas with it. Theflow-controlling valve 72 is closed by the data acquisition and controlunit 8 (see FIG. 6) when the desired charge of gas is present in theisotope ratio analyzer 24 (see FIG. 6). Then, the data acquisition andcontrol unit 8 (see FIG. 6) initiates an isotope measurement of the CO₂in the isotope ratio analyzer 24 (see FIG. 6). Again, measurement datagenerated by the IRGA 4 and isotope ratio analyzer 24 is acquired andstored or transmitted by the data acquisition unit 8. The whole sequenceof events can be repeated either immediately, or after a delay period asdictated by the program loaded into the data acquisition unit 8.

The operation of an embodiment of the cryogenic trap apparatus 82 shownin FIG. 10 (together with the sample conditioning unit 18 of FIG. 9), isas follows. With the liquid nitrogen dewar 112 filled to approximately75% capacity, the data acquisition and control unit 8 (see FIG. 6) cancontrol the temperature conditions of the U tube 108, in order to eithercryogenically trap a gas sample which is condensable at liquid nitrogentemperatures, or thaw a previously trapped sample.

Under the control of the data acquisition and control unit 8 (see FIG.6), when a sample is to be trapped, solenoid valve 102 is opened and nocurrent is passed through the resistance heater wire 106. This actionallows any nitrogen gas or air trapped in the upper part of cylinder 110to escape through vent tube 100, through solenoid valve 102, and out ofexhaust tube 104. The gas escaping from the upper part of cylinder 110,in turn allows the liquid nitrogen level in the cylinder 110 to rise tothe same level as that of the dewar 112, thus immersing the lower partof the U tube 108 in liquid nitrogen. As long as these conditions exist,the U tube 108 will remain at liquid nitrogen temperatures and any gasflow through the interior of the U tube 108 will liquefy or freeze if itis condensable at liquid nitrogen temperatures. When a sample is to bethawed or when the non-trapping state is required, the data acquisitionand control unit 8 (see FIG. 6) closes solenoid valve 102 and appliespower to the resistance heater wire 106. The current passing through theresistance heater wire generates heat and starts to evaporate nearbyliquid nitrogen. The nitrogen gas thus generated cannot escape from theupper part of the cylinder 110 since solenoid valve 102 is closed andthe result is that the liquid nitrogen level inside the cylinder 110 ispushed down below that of the dewar 112. The liquid nitrogen levelinside the cylinder 110 continues to be pushed down by the nitrogen gasuntil it is close to the bottom edge of the cylinder 110. As long assolenoid valve 102 remains closed and current passes through resistanceheater wire 106, the liquid nitrogen level inside the cylinder 110 willremain below the U tube 108. The heat generated by the resistance heaterwire continues to heat the U tube 108, providing enough energy to evolveany gases previously trapped in the interior of the U tube 108. Thepower applied to the resistance heater wire 106 by the data acquisitionand control unit 8 (see FIG. 6) can be modulated in order not raise thetemperature of the U tube 108 so high that it radiates excessive heatand boils liquid nitrogen unnecessarily.

The operation of an embodiment of a variable bellows apparatus 83 shownin FIG. 11 (together with the sample conditioning unit 18 of FIG. 6),and used in a batch mode embodiment is as follows. With the variablebellows 83 open to maximum extent, the data acquisition and control unit8 (see FIG. 6) can control the volume of the variable bellows in orderto reduce the sample size of a sample gas in which the concentration ofCO₂ is too large, for example in the case of analyzing pure CO₂, and maynot fall within the concentrations over which the analyzer has beencalibrated. To one skilled in the art of gas handling for isotopicanalysis this procedure is well understood (Werner and Brand 2001).However, in the present case, a number of calibration curvesspecifically for ¹⁴CO₂ and ¹³CO₂ over a range of concentrations of CO₂in air, for example from 10⁻¹⁰% CO₂ to 100% CO₂, may be required. Theuse of the bellows to reduce the sample size to within the range of themost favorable accuracy and precision of the analyzer (e.g., ¹³C, ¹⁴C)is a convenient method for this purpose.

Initially, solenoid valve 66 and flow-controlling valve 72 are closedallowing no gas to flow through them. Under the control of the dataacquisition and control unit 8 (see FIG. 6), the solenoid valve 66 isopened and power is applied from power supply unit 14 (see FIG. 6) topump 30 (see FIG. 6). The data acquisition and control unit 8 (see FIG.6) also sets the bellows 83 into the non-trapping state so that gas canflow freely through the cryogenic trap.

Next, gas present at gas inlet tube 2 (see FIG. 6) is drawn into andthrough the IRGA 4 (see FIG. 6), through the coupling tube 5, throughthe gas inlet tube 64 and through the solenoid valve 66. The gas is thendrawn through coupling tube tee 68, bellows 83 and through the gasoutlet tube 84. The gas flow then continues through the coupling tube 7(see FIG. 6), isotope ratio analyzer 24 (see FIG. 6), coupling tube 9(see FIG. 6), pump 30 (see FIG. 6), and out through the vent tube 33(see FIG. 6). When enough gas has been drawn through the bellows 83 topurge any gas remaining from a previous measurement, the dataacquisition and control unit 8 (see FIG. 6) sets the bellows 83 into thegas capture mode in which case switching valve is set to the closedposition for both ports allowing the gas to expand into the bellows andassociated pipe connections without being pumped away. After a period oftime that is sufficient for the gas to equilibrate in the volume of thebellows, the control unit 8 (FIG. 6) is set to close the bellows by someamount so as to reduce the bellows total volume. At the same time pipingvolumes 68, 86 and 84 are open to vacuum to flush out any remaining gas.

After pumping for a suitable period valve 66, 72 are closed and fullyevacuated. At this time the control unit 8 (FIG. 6) opens port to allowgas in bellows to expand into the piping volume. The control unit thenprovides for closure of the bellows valves and the system is pumped outas before reducing the sample size. The control unit 8 (FIG. 6) thenproceeds to repeat the procedure until the sample gas pressure isconsistent with pressures that are optimal for analysis and comparisonwith the relevant calibration curves. Then, the data acquisition andcontrol unit 8 (see FIG. 6) initiates an isotope measurement of the CO₂in the isotope ratio analyzer 24 (see FIG. 6). Again, measurement datagenerated by the IRGA 4 and isotope ratio analyzer 24 is acquired andstored or transmitted by the data acquisition unit 8. The whole sequenceof events can be repeated either immediately, or after a delay period asdictated by the program loaded into the data acquisition unit 8.Manipulation of sample gas pressures for analysis in a three cell systemis a critical performance factor given the vast differences inconcentration between ¹⁴CO₂ and ¹³CO₂.

In further embodiments, the sample gas mixture can be provided fromliquid or solid samples. The solid and liquid samples are turned into agas via heating or through combustion. The sample gas mixture can beprovided from any one of a number of commercially available devicescapable of generating gases from non-gaseous samples in order tofacilitate gas concentration or gas isotope ratio measurements. Forexample, a Dumas combustion device such as the one manufactured by CarloErba could be connected to the gas inlet and the gas mixtures generatedfrom the combustion of solid sample materials analyzed in a similarfashion to those previously described.

In further embodiments data captured by the device is transmitted viatelemetry to one or more central locations for analysis and datasummary. The data thus can be used to construct national, regional andstate wide budgets or as the case may require. FIGS. 24-29 showinternational (EU), national US) and state wide grids as examples ofdevice locations offering the capability of real-time, simultaneousmeasuring, monitoring, reporting and verification of ¹³C and ¹⁴C inatmospheric CO₂ all defined against a single standard common to alldevices. FIGS. 16, 17 and 18 show embodiments in which devices in thefield transmit data to a satellite or other means after which the dataare analyzed and summarized to comply with voluntary and/or regulatorypolicies as well as for use in carbon trading platforms as described inFIG. 19.

Applications of the System of Systems

In certain embodiments, a novel reporting system for isotopicallydefined carbon emissions can be used in the context of greenhouse gastrading and carbon based financial instruments. The measured values for¹³C and ¹⁴C of CO₂ can be used in conjunction with flow and volumemeasurements to derive a total emissions value for liters (moles)emitted CO₂ (and well known conversions thereof to C emissions units).

A Two Carbon Trading Paradigm: Applications of the System of Systems

In certain embodiments, a novel reporting system for isotopicallydefined carbon emissions can be used in the context of greenhouse gastrading and carbon based financial instruments. The measured values for¹³C and ¹⁴C of CO₂ can be used in conjunction with flow and volumemeasurements to derive a total emissions value for liter (moles) emittedCO₂ (and well known conversions thereof to C emissions units, such asmetric tons, CO₂ and carbon equivalent units). For example, in the caseof measurement of isotopic values where total volumes (moles) from oneor more sources can be calculated, then the respective percentages ofbiogenic and fossil fuel derived CO₂ can be known. In at least someembodiments, the monetization of emissions using a system of systemsdisclosed herein also reports the emissions data in a way that clearlydesignates the components of interest. For example, in a case where 80%of emissions are fossil fuel derived and 20% are biogenic derived, thenas sourced by their respective isotopic components, one can designatesuch data as follows:

¹⁴C units: 80

¹³C units: 20

Thus, as the isotopic data are converted to volumetric and molar data,the same designation may be used to report metric tons of the respectivecomponents. For example, following from the above example, if thecalculation of metric tons results in 800 for fossil fuel and 200 forbiogenic carbon, respectively (the numbers are for illustration purposesonly), then the units of carbon emissions may be reported as follows:

¹⁴C mt: +800

¹³C mt: +200

In the above designations, one can see the value in making explicit datafor carbon emissions trading available as to the source of the carbon inquestion. Currently, emissions are typically estimated, thus, thechanging components of fossil and biogenic CO₂ are not currentlyincluded in trading mechanisms.

The above approach will be useful in designating the sequestered carbonin forest activities, for example. By way of illustration, sequesteredcarbon may be quantified as follows:

¹⁴C mt: −200

¹³C mt: −600

In the above example, the data clearly indicate the forest in questionhas drawn down some 200 metric tons of fossil fuel derived CO₂ and some600 tons of biogenic derived CO₂.

Representing carbon emissions and sequestration data in this way for allcarbon units could add considerable value to the units of carbon andprovide new dimensions in pricing.

In the cases as described above, designations as suggested could bederived over any time period and over any spatial scale (according tothe placement of multi-isotopic units across the space in question),rendering values directly compatible with the “metric tons carbon” andmetric tons “carbon equivalent” units used in all carbon tradingplatforms to date. Thus, a system of systems according to certainembodiments offers a new way to monetize carbon emission andsequestration data based on actual measurements. The multi-isotopicapproach used here provides for a novel way to report carbon emissiondata (either as sink or source), offering new dimensions in carbonpricing, carbon trading and greenhouse gas policy considerations.

In summary, a laser based system of systems for both ¹³C and ¹⁴C offersmany benefits over the traditional IRMS and AMS methods. Mostimportantly, samples can be analyzed and referenced to an instrumentstandard(s) in situ—there is no need for transport of gas sample tocentral laboratories. Secondly, the sample is measured as free CO₂ inair and does not require a cryogenic collection step, thus the sample isanalyzed in a non-destructive manner and may be repeatedly analyzedand/or analyzed for longer periods of time to increase data collectionand statistical certainty. Thirdly, the data for ¹³C and ¹⁴C can becompared with a variety of standards in a single instrument, or externalto the instrument, and also can be compared with ensembles ofinstruments in any location around the world, instantaneously, ensuringcomparability across all samples regardless of location. As disclosedherein, the fabrication of large numbers of sealed reference cells canbe made according to methods that are familiar to those skilled in theart of making CO₂ gas filled lasers such as those produced by AccessLasers, Inc., CA, or LTG-Lasertech, Concord, ON. Thus, referring to FIG.12 the use of sealed-cells that contain or can be made to contain thesame standard gas and employed in large numbers of instruments vastlyimproves reference gas statistics compared to reference systems oftypical isotope ratio mass spectrometers and accelerator massspectrometers. The near-simultaneous acquisition of reference data andunknown data also provides short and long term stability of analyzersignals.

Again referring FIG. 12, the laser based spectroscopy approach alsopermits an optional hierarchal verification of instrumental standardsealed cell performance by comparison with sealed cells containing avariety of standard gases external to the actual data producingmulti-isotopic analyzers. External instruments or modules that containonly primary sealed cell references can be in a single, double or triplecell configuration and would operate essentially like theirmulti-isotopic analyzer counterparts that also contain flow-throughsample cells for analysis of unknowns. Because the external referencecell unit does not contain sample cells, but is otherwise equipped withdata collection and telemetry features, the external reference unit canbe used to compare reference signals and baseline signals with any othermulti-isotopic analyzers by telemetric communication. Additionally, aseries of standard cells for both ¹³C and ¹⁴C and the appropriate laserscould be deployed as a payload aboard satellites communicating withensembles of instruments around the world. Such an arrangement ofsatellite based and ground based systems that are locked into standardreference frameworks offer capability to structure live trading ofinstantaneous carbon credits as data are collected in a real-timeanalytical and reporting mode. Additionally, such satelliteconfigurations for the ¹³C and ¹⁴C standards and data collection couldalso be used to cross-compare data collected by greenhouse gas observingsatellites for carbon emissions and other greenhouse gases (e.g.,Orbital Carbon Observatory) with ground based measurements as proposedherein. Thus, an instrumental approach that reduced isotopicfractionation, provided for stable and homogeneous standards across timeand space and that carried out analyses in situ that are referenced withexternal standards linked in a global network would be highly desirablefor reliable and transparent baseline data for all carbon tradingplatforms as well as offer the potential to integrate and comparespace-based observations of carbon emissions.

The following examples are illustrative and not limiting.

Example 1 Forest Trading

Referring to FIG. 23 an example application of the system of systems isprovided. While numerous locations within forests are measured andmonitored for CO₂ concentration, isotopic composition to determine andquantify source terms for CO₂ to support carbon trading has not beenreported. Specific cases are used herein for illustration.

Currently, forest carbon flux is estimated using a variety of forestryalgorithms such as described previously by the Chicago Climate Exchange(CCX, www.ccx.com). However, research projects quantify carbon exchangeon a limited basis. By way of background one of the projects is brieflydescribed. The forest measured and monitored for carbon flux in thisexample is described in Barford, et al., 2001, and presents anopportunity to apply the system of systems to real data for forestcarbon flux but lacking isotopic data to identify and quantify sourcesof CO₂. The site, located in western Mass., is equipped with a talltower extending 30 m from the ground and equipped with appropriateinstrumentation. The eddy covariance technique, known well to thoseskilled in the art, is used to measure fluxes of CO₂, momentum, andsensible heat and latent heat at 8 levels. Isotopic data acquisition isselected to match the acquisition rates of high frequency transport fluxof the atmosphere. The use of the eddy covariance technique imposesconsiderable technical difficulties on isotopic instrumentationincluding (e.g., Salesk et al., 2006): 1) rapid response time (<1 secondfor analysis of ¹³CO₂), 2) sensor stability allowing continuousmeasurements without baseline drift enabling capture of thelow-frequency wind transport flux, 3) high precision such that smallvariations in the eddy flux isotopic signal can be resolved. Thecorresponding units for carbon isotopic eddy flux are given as ppmmeters s⁻¹ per mil. Such measurement challenges for isoflux are on theorder of <0.1 per mil, standard deviation of 10 second integrationtimes, along with stable baseline data. The aforementioned eddycovariance approach must operate 24 hours a day throughout a period ofone year to obtain a net flux of carbon in a given forest area. In thisway, winter release of CO₂ via respiration is compared to summer drawdown of CO₂ by photosynthesis: the net difference will determine if theforest is a sink (i.e. negative number) or a source (i.e., positivenumber). Thus, accurate and reliable forest flux data that could be usedfor carbon trading can be obtained using a highly demanding set ofinstrument function and software protocols. According to the data ofBarford et al. (2001) over a period of 8 years the forest sequesteredapproximately 2 megagrams or metric tons of carbon per hectare, however,no correction is made for the presence of fossil fuel CO₂ that was takenup by plants and measured as part of the routine measurements forconcentration, thus representing an unknown error. In the case in whichthis is used to price and trade carbon in metric tons, then, anunavoidable and unknown uncertainty exists. The Barford et al. (2001)data were collected with a small footprint tower of approximately 30meters in height being sufficient to be above the canopy. A series oftower heights is desirable as the taller the tower the larger thefootprint.

The measurement approach and methods used in this study suggest that thefootprint of the Barford et al. (2001) data represent some 100-200hectare. We take the lower case of 100 hectares as an example, meaningthat the 100 hectares are defined by property lines or other means.According to the data, approximately 16 megagrams accumulated over the 8year period resulting in 16 metric tons per hectare of sequesteredcarbon. If a metric ton of carbon were traded at the end of the eightyear period for $20 per ton then the owner of the land would havecredits worth $32,000. However, if the uncertainty was 10% then thepricing could be over or under priced by $3,200. Thus, without the useof a ¹⁴C and ¹³C analyzer, there is no way to disentangle fossil fuelcontributions from natural and plant based contributions. Whenconsidering 10's to 100's of millions of acres potentially involved incarbon trading one can see that economically significant errors arepresent. The data for Barford et al., (2001) clearly demonstrate thatyearly net flux data are required as the values for each year can besignificantly different. For example, the year 1998 of the Barford etal. (2001) data show that carbon sequestration (net carbon uptake MgCha⁻¹ yr⁻¹) was reduced by 2.4 megagrams compared to the preceding yearof 1997. The record reported by Barford et al. (2001) shows from 0.2 to2.4 Mg variation across a measurement period from 1993 to 1999. Thus,this data set along with others (e.g., Scott et al., 2004) illustratethe need for full measurement of forest carbon flux with fine timeresolution to allow eddy covariance applications and to ultimatelyprovide carbon storage data that highly reliable, inter-comparable withother projects and have a defined uncertainty of approximately <0.1 MgCha⁻¹ yr⁻¹.

According to the data of Scott et al. (2004) use of eddy covariancemethods may also be used to establish criteria for carbon fluxassociated with harvesting of forest for the production of wood products(e.g., paper, wood building products). Since many forests may support awood products industry the use of the eddy covariance technique can beused to ensure that carbon replacement by tree regrowth is attained.Thus, a simple mass balance of carbon lost after harvest and carbonsequestration after cutting over a period of years can ensuresustainability of the forests while allowing wood products inventory.The rate of tree regrowth will determine the time period required toreplace the carbon removed. Thus, using the systems of systems andplacing ensembles of analyzers in areas where forest harvest andre-planting takes place offers a unique method for establishing thecarbon dynamics and associated pricing of forest credits under a varietyof circumstances.

We note that errors associated with estimation methods as reported byGalik et al. (2009) with reference to the generation of forest carbonoffsets are shown to be as high as 30%. The sensitivity of forest modelsaccording to Glaik et al. (2009) is related to the treatment of forestcarbon components that are comprised of a number of carbon poolsincluding above ground and below ground active components, forest litterand dead trees. The isotopic approach with eddy covariance describedhere includes the primary below ground and above ground biomass andtheir dynamic carbon uptake and release.

In one embodiment following on from the above example, we refer to FIG.23 showing an array of 20 GMPs positioned across the landscape at 100hectare grid lines. The GMP analyzes gases taken at several levels ontowers or other structures allowing the eddy covariance application.Thus, using the example above as a reference, we take for illustrationan eight year period in which each 100 hectare plot sequestered 16metric tons of carbon. However, in this case the system of systems:

-   -   1) Provides ¹⁴CO₂ signal for fossil fuel CO₂, ¹³CO₂ signal for        biogenic CO₂ and total ¹²CO₂ measured at a rapid rate of        approximately 1 to 10 Hz ideally but also may be up to 100 Hz,        allowing integration with eddy covariance methods.    -   2) Provides for an inter-calibrated network of analyzers to        ensure comparable results for each device. Placement of GMPs        will be such that dispersion on scales of 1 to 100 kilometers is        within the detection range of the GMPs being 2 per mil for ¹⁴C        and 0.1 per mil for ¹³C. Initial testing with various placement        patterns may be required to derive the optimal number and        configuration of analyzers. Height of sample intakes should be        at least several meters above the tree canopy, with some        instruments being placed higher (e.g., 50 meters). A mix of        tower heights may be used to discern wider areal carbon flux        footprints. Towers utilized currently range from approximately        30 meters to a small number of tall towers at 400 meters.    -   3) Provides for a telemetry system to transmit data to a central        location.    -   4) Provides for data analysis and model integration.

The data collected would then consist of ¹⁴C and ¹³C delta ratios andthe CO₂ concentration. Hypothetical measurements are shown in FIG. 23consisting of total CO₂ concentrations (solid line, top), delta ¹³CO₂ratios (middle small dashed line) and delta ¹⁴CO₂ ratios (long dashline, bottom panel). Note that the CO₂ concentrations rise and fallaccording to the seasons (marked S for summer and W for winter). Thetotal CO₂ concentration does not allow determination of the fossil fuelcomponent. Moreover, as was demonstrated in FIGS. 1 and 2, ¹³CO₂ ratiosalso do not distinguish fossil fuel contributions to the carbon exchangeand thus the net carbon gained or lost. The gain or loss then representsthe carbon component that is either source or sink, or in trading terms,a carbon credit lost (source) or a credit gained (sink).

The signal frequency of 10 Hz is important for eddy covariance data.Data rates at longer than 1 second will not meet the requirement tomatch transport flux of wind and thus cannot be effectively used foreddy covariance preventing a high resolution and accurate record ofcarbon flux. Thus, one skilled in the art of such measurements willrecognize that the widespread use of isotopic analysis with eddycovariance is restricted to a few sites with limited measurement timesalthough networks of such towers where the eddy covariance method isused with CO₂ concentrations alone is approximately several hundredstations as part of the Fluxnet project (FLUXNET 2009), Thus, anapplication of the “system of systems” approach disclosed herein isrecognized as much needed but as yet not implemented.

Thus, when CO₂ is drawn down in summer, as plants grow, the ¹³CO₂ ratiosdecrease due to a fundamental discrimination against the heavier ¹³CO₂molecule. The trend in ¹⁴CO₂ may also become less positive since fossilfuel does not contain ¹⁴C thus diluting the current ¹⁴CO₂ background.However, the raw data for each of the terms (total CO₂ concentration,¹³CO₂ and ¹⁴CO₂ ratios) can be used in a series of calculations known tothose skilled in the art to derive source data of fossil andbiologically derived CO₂. As described previously, such simple treatmentof isotopic data are not adequate to support carbon trading, lackingsufficient numbers of analyzers, inter-calibration and an appropriatemodel integration over a representative area. For illustration anexample of a simple calculation deriving the fossil fuel componentdescribed by Levin, 2008 is provided:

To estimate regional fossil fuel CO₂ from measured ¹⁴CO₂ and CO₂concentration one can use the following mass balance equations:

CO_(2 measured)=CO_(2 biological)+CO_(2 background)+CO_(2 fossil fuel);and

CO_(2 measured) (δ ¹⁴C_(measured)+1000‰)=CO_(2 background)(δ¹⁴C_(background)+1000‰)+CO_(2 biological) (δ¹⁴C_(biological)+1000‰)+CO_(2 fossil fuel) (δ ¹⁴C+1000‰)

In the above equations, CO₂ measured is the observed CO₂ concentrationsfrom the network of devices, CO₂ background represents the concentrationof CO₂ at a reference clean air site (e.g., Globalview 2006), CO₂biological is the regional biogenic component, and CO₂ fossil fuel isthe fossil fuel component for the region of the measurements. The¹⁴C/¹²C ratios of these components in the delta notation arerespectively, delta ¹⁴C measures, delta ¹⁴C biological and delta ¹⁴Cfossil fuel. Delta ¹⁴C is the ‰ deviation from the ¹⁴C/¹²C ratio fro theNBS oxalic acid standard activity corrected for decay (Stuiver andPotlatch 1977).

Thus, solving for CO₂ fossil fuel yields the following equation:

CO₂ fossil fuel=[CO_(2 background)(δ ¹⁴C_(background)−δ¹⁴C_(biological))−CO_(2 measured) (δ ¹⁴C_(measured)−δ¹⁴C_(biological))]/δ ¹⁴C_(biological)+1000‰

For example, if the mean contribution of fossil fuels were determined tobe 1 ppmv of the total CO₂ measured for the land within the array, thenusing the data from Barford et al., 2001, an error of approximately 10%would be unaccounted for amounting to 1,440 metric tons of CO₂ stored asopposed to 1,600 metric tons. On a dollar volume basis, a difference of$3,200 would have been in error. On larger scales such as thoserepresented by states and over larger regions such errors will becompounded. For 2008, according to the reporting agency, Point Carbon(www.point.carbon.com) the total dollar volume of carbon tradingrepresenting all carbon financial instruments was approximately $129billion US, primarily as a result of trading within the European Union.Thus, a 10% error, if representative, amounts to approximately $12.9 USbillion dollars. The complexity of the data produced utilizingmulti-isotopic analyzers is illustrated in FIG. 23 and clearly requiresappropriate data-model integration to derive total carbon for the 100hectare area. A system of systems as disclosed for the purposes ofcarbon trading requires integrated components at various scales from theanalyzers to data analysis and synthesis as shown in this example.

Accordingly, as shown in FIG. 24, the GMP devices could be placed acrosscountry scales utilizing existing towers and other structures to reachabove the ground , as in the case of the US and across state wide scalesas shown for the state of Maine (FIG. 25). FIG. 26 shows a system ofsystems placement for the Regional Greenhouse Initiative representingthe northeast US. FIG. 27 shows a system of systems placement for theMidwest Greenhouse Gas Accord. FIG. 28 shows a system of systemsplacement for the Western Climate Initiative. FIG. 29 shows a system ofsystem placement for the European Union Exchange Trading Scheme forgreenhouse gases. For the purposes of illustration only the GMP devicesare placed roughly at 5 degrees×5 degrees intervals in latitude andlongitude or in other configurations as determined necessary accordingto initial placement of analyzers and other factors. Towers of varyingheights may also be used to capture additional data for isotopic flux asa function of height.

Example 2 Soil Carbon Trading

Referring to FIG. 30 another embodiment of the system of systems isprovided. The soil reservoir of carbon far exceeds that of the standingbiomass and in some respects may be more labile than that of thestanding biomass. The warming of higher latitudes as predicted by modelsof the biosphere under increasing CO₂ and consequent surface warmingsuggest that large amounts of previously sequestered carbon may bereleased. The release of carbon in the soil is primarily determined bysoil moisture and temperature (Amundson et al., 2008) and thus is likelyto be highly heterogeneous across the landscape depending on a host offactors. For these reasons soil flux should be determined and measuredin a wide variety of sites to detect soil release in relation to globalwarming. Moreover, efforts to sequester carbon in soils ranging fromagricultural to prairie lands are eligible for carbon trading offsets(CCX 2010) but are based on gross oversimplifications and estimates. Asystem of systems as described herein:

-   -   1) Provides ¹⁴CO₂ signal for fossil fuel CO₂, ¹³CO₂ signal for        biogenic CO₂ and total ¹²CO₂ measured at specified time        intervals of approximately 1 sample per minute as integrated        with soil flux chambers and soil probe gas sources. Eddy        covariance towers shall also be used as described above for the        forest sampling with a sample frequency of from 1 to 10 Hertz        ideally but may be up to 100 Hz. As for the forest carbon        GMP—eddy covariance set up, such applies to the soil sample        chambers and soil probes.    -   2) Provides for an inter-calibrated network of analyzers to        ensure comparable results for each device. The placement of soil        gas chambers and probes can be according to a statistical        analysis for the area to ensure representative data. Number,        heights and configuration of eddy covariance measurements can        depend on factors such as topography, strength of diurnal CO₂        fluctuations and wind patterns. However, tower heights may be        relaxed in settings where the vegetation cover is close to the        surface as in grasslands, prairies, etc. ranging from several        meters to 30 meters.    -   3) Provides for a telemetry system to transmit data to a central        location.    -   4) Provides for data analysis and model integration.

Much as the measurement of total CO₂ in the atmosphere does not revealsources (sinks) of the CO₂, the soil CO₂ atmosphere also does not revealsource components in relation to total CO₂. In the case of the soil,however, the various carbon (referring to FIG. 30) sources of interestrelate to the age of the carbon rather than to a distinction betweenbiogenic versus fossil carbon. Specifically, the large scale release ofvery old soil carbon in the age range from 2 to 8,000 years ago wouldsignify that previously sequestered carbon is subject to release andwould potentially portend a large source of carbon to the atmospherethat could have significant consequences for the radiative budget of theatmosphere.

A number of well developed technologies exist to automatically sampleabove ground soil gas for integrated soil flux. Such a device ismanufactured by LI-COR Bioscience Corp., Lincoln, Nebr., modelLI-8100-101 and LI-8100-104, Automated Soil CO₂ Flux System. The devicenamed is specifically designed for multiple chamber use, offering highspatial and temporal resolution of soil CO₂ flux rates. The systemfeatures chambers that automatically open and close at specifiedintervals to avoid artifacts from CO₂ absorption and leakage over longtime periods caused by small pressure changes. Such chambers as sold byLI-COR can be operated remotely in windy and/or calm conditions.

In addition to the soil gas monitors, placement of eddy covariancesetups is also required to document accumulation of soil gas in the nearsurface environment. Accordingly, sampling rates for eddy covariance canbe rapid at <1 second. Thus, such as system of systems incorporating theLI-COR devices in conjunction with the GMP and located in ensembles andfurther supported by eddy covariance methods will be highly valuable indetermining the release or sequestration of carbon for a given area.

Additionally, commercial devices for sampling the CO₂ soil atmosphere atdepth are also available such as that described by Vaisala, Inc., ModelGMP3431 carbon dioxide probe, operated in flow through mode. Inpractice, those skilled in the art of sub-soil gas sampling recognize anumber of approaches in capturing gas samples at depth for analysis.

Thus, as shown in FIG. 30, a GMP unit 600 coupled to any number of soilsampling chambers at the surface 601 and/or to any number of sub-surfacesampling systems 602, 603 and 604 combined in a sample manifold 605could detect singly and across a landscape the soil carbon release orsoil carbon sequestration. The above soil flux chamber 601 provides anintegrated soil gas sample resulting from the entire soil column 609 andthus represents an average of soil gas composition. Soil probes atdifferent depths 602, 603 and 604 integrated with a sample manifold 605provides soil gas composition characteristic of each soil layer. Modernsoil 606 will contain higher concentrations of ¹⁴C than older soils 607and 608 at greater depths in the soil column. In this particularillustration, soil isotopic carbon flux can be measured directly bycombining soil flux rates given as quantity of CO₂ fossil and biogenicreleased from a given area over a defined period of time. Accordingly,use of appropriate models such as described in Amundson et al., 2008 canbe used in conjunction with isotopic data to derive metric tons ofcarbon as released or sequestered. As indicated above, the use of eddycovariance can integrate the accumulation of gas from the soil and gasin the near surface environment to fully define the carbon flux for agiven area over a given period of time.

The system of systems approach as described herein can be used tomeasure and monitor soil CO₂ flux in relation to soil conservationstrategies such as no till methods and replanting of barren soils (e.g.,Schlesinger 2000) and thus provides a critical means of defining thecapacity of a given soil for carbon sequestration under a variety ofconditions. Such a system of systems is clearly needed for soil carbonmeasurements. As described previously, the Chicago Climate Exchangeprovides estimated rates of sequestration for large tracts of land basedon models alone (CCX 2010). Such models do not take into considerationfactors such as soil moisture, changing surface temperature andapplication of nutrients as fertilizer and thus creates uncertaintiesthat can lead to erroneous carbon metrics for soil carbon trading. Theuse of the system of systems as disclosed herein presents a means toreduce such uncertainty and result in verified carbon fluxes that maythen be used to enter the soil carbon market. The use of the system ofsystems as disclosed herein could provide several types of soil carbonfinancial products such as soil carbon flux as related to specific landmanagement practices (e.g., planting of particular species of plant,tillage method, nutrient application, etc.). As described above forforest carbon trading, the system of systems can be used to quantifycarbon dynamics in areas where a variety of soil and vegetationmanagement practices are employed for industry and/or according to soilecosystem type.

Example 3 Agricultural Emissions Trading

Referring to FIG. 31 another embodiment of the system of systems isprovided. According to FIG. 31, agricultural fields 350 are defined in agiven location. In the center of any given field or series of fields aneddy correlation flux tower 351 is established that:

-   -   1) Provides ¹⁴CO₂ signal for fossil fuel CO₂, ¹³CO₂ signal for        biogenic CO₂ and total ¹²CO₂ measured at a rapid rate of        approximately 1 to 10 Hz ideally but up to 100 Hz allowing        integration with eddy covariance methods.    -   2) Provides for an inter-calibrated network of analyzers to        ensure comparable results for each device. Configuration and        heights of towers for eddy covariance will provide for extension        above the crop surface and thus may range from several meters to        30 meters with the number of GMPs determined by the signal        strength, wind patterns and other factors providing detection        capability of the isotopic signature for agricultural carbon        cycling. Initial placement of the GMPs may be needed for optimal        placement of GMP analyzers.    -   3) Provides for a telemetry system to transmit data to a central        location.    -   4) Provides for data analysis and model integration.

Currently, verification of agricultural carbon exchange and storage isone of the most difficult areas of endeavor. The difficulty is easilygrasped when one considers that plants are grown on an annual orsemi-annual basis and then removed from the land surface. Thus, a fullaccounting of carbon budgets for agriculture must take into accountbiomass removed from the land and replacement of that land with new cropcover. In addition, agricultural practices by their nature involvedigging up and in many cases turning over soil allowing volatile soilcarbon components to be released to the atmosphere by oxidation. Inaddition, the use of fertilizers are also considered in the overallbudget terms, since fertilizer is applied with a cost to the grower andits production involves generation of greenhouse gases. In this caseagain, while large areas of agricultural land may be planted with onecrop, each such area of different crops is provided with an eddycovariance system of systems. Accordingly, verification measuresutilized by the CCX (CCX 2009) for example, lack precision and areapplied blindly to all soils despite obvious differences in planting andharvesting specifics and thus are uncertain potentially resulting incarbon trading errors that could be minimized by use of a system ofsystems approach as disclosed herein.

Another approach involves models that are parameterized with any numberof soil data sets representing field sample analyses over large areas.One such product, C-Lock (Updegraff et al., 2005) employs such a system.Carbon sequestration rates are essentially classified into no-till andconventional tillage and applied blindly across large areas of land. TheC-Lock approach is based upon a soil organic carbon model known asCentury (Parton et al., 1993) and is used without further examination ofsoil carbon content of the factors that may alter such content includingvariations in climate factors of rainfall, vegetation change and landmanagement. Thus, as with forest carbon flux and its relation to carbonpricing, the agricultural carbon financial products as described hereinare not known or suggested and no system of systems to measure, monitor,verify and account for carbon flux has been implemented.

According to an embodiment of the system of systems herein disclosed, aset of monitoring stations placed within the sample grid of agriculturalland can be collected as described earlier. A commercially availablesystem, such as the eddy covariance system available from CampbellScientific, UK can be deployed and integrated with a GMP ¹³C and ¹⁴Canalyzer at intervals of from 100 meters squared to 1000 meters squaredand multiples depending on the size of the agricultural area to bestudied. An inventory of ¹³C, ¹⁴C and CO₂ concentrations are acquired asdescribed earlier. In this case, biomass harvested quantified by weightand soil organic carbon at intervals to match the GMP device placementcan be measured by standard soil analysis techniques; all practicesknown to those skilled in the art of agricultural and soil management.Thus, application of the system of systems in conjunction with knownmodels of agricultural management can reduce uncertainties for carbonmetrics required for carbon trading representing a variety ofagricultural practices.

We note here that recommendations and requirements for agricultureemissions reductions provided by the CCX (CCX 2010) focus on destructionof methane produced by manure digesters. In the case of a small singlepoint source, methane destruction is verified by flaming of methane atthe vent. However, we note above the larger issues of carbon flux fromagricultural areas are treated as estimates and thus prone to error. Inthe case of ruminant management we note that the addition of nutrientsfrom manure to the landscape is not taken into account even though it isclear that emissions from land managed in relation to ruminantmanagement must also be considered. While the embodiments describedherein provide examples for CO₂, the system of systems is applicable toany greenhouse gas such as methane and nitrous oxide.

Example 4 Carbon Emissions Trading for Bodies of Water (e.g., Ocean)

Referring to FIG. 32, an embodiment suitable for determination ofoceanic carbon exchange is described. There is considerable interest insequestration of carbon by the ocean induced by iron oxides placed insurface waters as a means of “ocean fertilization.” Ocean ironfertilization works by improving the efficiency of natural phytoplanktonproduction in the open ocean. Phytoplankton are responsible forapproximately half of the world's annual CO₂ absorption capability. Asthey continually bloom, mature and die in a 60-day lifecycle, a portionof their biomass sinks to depth, locking away carbon for long periods oftime. This process, called the “biologic pump,” is one of the oldestecological mechanisms on Earth. Over the last several hundred millionyears it has helped concentrate nearly 90% of all mobile carbon in thedeep ocean as sediments and dissolved bicarbonates. However, as amechanism to sequester carbon directly from the atmosphere themeasuring, monitoring, verification and accounting of carbon sequesteredfrom iron fertilization has not been implemented.

In several respects the ocean has been treated like the world's forestsaccording to the Kyoto Protocol in that the worlds oceans are notincluded as eligible for carbon credits even though the oceans are amajor source and sink of CO₂. While the dangers of altering largeportions of the natural ocean carbon cycle are real and should beconsidered a geo-engineering effort, a primary impediment to carbonreduction via the ocean is also related to a lack of carbon flux datafor the worlds' oceans and the capability to closely measure and monitorchanges in the oceans' carbon flux. The GMP system of systems can bedeployed in much the way as they are for the forests. Instead of towersto support GMP ensembles, ocean buoys could be used as surface monitorsand could be equipped with sampling hardware to sample water at desireddepths. As for forests, the ¹³C and ¹⁴C isotopic composition of carbonin seawater are key diagnostics that indicate the functioning of theoceanic carbon dynamics (e.g., Cias et al., 1995; Broecker 2007). In thecase of ¹⁴C a transient ¹⁴C signal as a result of the hydrogen bomb usecreated a pulse of manmade ¹⁴C which provides a convenient signal tomeasure rates of carbon flux in the ocean. In the case of ¹³C, seawaterbiology fractionates ¹³C during photosynthesis and respiration in amanner similar to that of terrestrial plants. However, as for theforests the oceans carbon dynamics are not measured with enoughfrequency or spatial coverage to provide a clear pattern and trend incarbon oceanic flux.

Several companies are seeking to commercialize the process (e.g.,www.CLIMOS.com) but have not proposed effective means to measure,monitor, report and verify emissions for carbon trading schemes.However, it is difficult to assess the effectiveness of oceanic carbonexchange and sequestration with ocean chemistry and stripping ofdissolved gases from ocean water. Typically, stripping of dissolvedgases from ocean water is a near automated process that results in flasksamples of gas similar to that obtained for whole air that are thenanalyzed individually using IRMS techniques. The system of systemsdescribed herein is readily applicable that:

-   -   1) Provides ¹⁴CO₂ signal for fossil fuel CO₂, ¹³CO₂ signal for        biogenic CO₂ and total ¹²C₂ measured at hourly intervals or less        with integration of a CO₂ extractor from seawater with a GMP and        ensembles thereof.    -   2) Provides for an inter-calibrated network of analyzers mounted        on ocean buoys to ensure comparable results for each device.        Placement on the surface can depend on signal strength and may        be determined by initial testing of configurations to        accommodate the signal and area of interest.    -   3) Provides for a telemetry system to transmit data to a central        location.    -   4) Provides for data analysis and model integration.

Thus, a system of systems could be operated remotely on an ensemble ofinstrument buoys covering specific oceanic areas to measure atmosphericgases in the upper part of the ocean. Gas selective membranes orautomated gas stripping devices would be employed to sample dissolvedocean gases as integrated with the GMP. A seawater CO₂ extraction deviceis commercially available from Axys Technologies, Sidney, BritishColumbia, model Greenhouse Gas Sentinel. Alternatively, the GMP isotopicanalyzer could be operated shipboard making essentially continuousmeasurements for ¹⁴C and ¹³CO₂ (e.g., McNichols et al., 2002). Referringto FIG. 31, seawater via an underwater inlet 300 is drawn into a gasextraction unit 301. The gas is extracted and conditioned as describedearlier by scrubbers and dryers and then is pumped into the isotopicanalyzer 302. Isotopic data and related sensor data are transmitted viathe onboard SCADA system 303. The buoys, gas stripping and relatedmethods are well known to those skilled in the art of oceanic gassampling. Thus, use of the system of systems will allow continuous,standards based, measuring, monitoring and reporting of carbon exchangein the ocean to quantify oceanic carbon sequestration as a result ofatmospheric mitigation strategies or as a result of changing globalconditions. The ocean, representing a large potential sink or source ofCO₂ is a critical area for quantification that could involve carbontrading.

Example 5 City Scale Carbon Emissions Trading

Referring to FIG. 33, an application to a city scale carbon budget forManhattan, N.Y. is illustrated. Greenhouse gas budgets of large citiesin some cases can account for a majority of emissions for a given stateor region. Thus, an approach that quantifies the emissions from cityscale activity could be highly valuable in an overall carbon budgetplan. Major sources of emissions in cities range from industrial(natural gas and fuels) to power generation (coal, fuels) to automobiles(gas, diesel). A city scale system of systems is readily applied to cityscale measuring and monitoring that:

-   -   1) Provides ¹⁴CO₂ signal for fossil fuel CO₂, ¹³CO₂ signal for        biogenic CO₂ and total ¹²CO₂ measured at a variety of locations        and elevations on an hourly or less sample analysis schedule.        Eddy covariance applications with sampling rates of 1 to 10 Hz        ideally but may be up to 100 Hz.    -   2) Provides for an inter-calibrated network of analyzers to        ensure comparable results for each device. Device placement may        depend upon suitable structures and proximity to borders, water        bodies, etc., but not less than 1 GMP per square miles and up to        1 GMP every 10 square miles of city landscape.    -   3) Provides for a telemetry system to transmit data to a central        location.    -   4) Provides for data analysis and model integration.

Referring again to FIG. 33, multi-isotopic analyzers are placed atapproximately 10 to 20 mile intervals along the coast of Manhattan witha additional analyzers as shown to capture emissions from the interiorof the city environment. As described in FIG. 2, a multi-isotopicanalyzer can differentiate sources of CO₂ from fossil and biogenicsources including differentiation of natural gas CO₂ from coal and autofuel CO₂. Such measurements can be used to quantify offsets inautomobile emissions, industrial emissions and use of solid fuels. Forexample, California's AB32 reduction plan involves substantial reductionof emissions from heavy duty tractors that pull 53 foot or longerbox-type trailers (www.arb.ca.gov). A system of systems provides anintegrated measure of such emissions for the city of Manhattan inaddition to sourcing of other emissions. Carbon emissions from theindividual-level activities of passenger transport and energy use inresidential buildings accounted for approximately 40 percent of all UScarbon emissions in 2005 (Brown et. al. 2001). Thus, a system of systemsas disclosed herein.

Absent an enormous leap forward in low-carbon energy technology, meetingthe challenge presented by climate change will require that individuals,households, and communities all become part of the process, withbuilding codes, transport infrastructure investments, and support fortransportation alternatives. Recognizing this, many cities havedeveloped climate action plans, containing a disparate mix of mostlyvoluntary greenhouse gas emissions reduction proposals. However, as hasbeen proposed by Salon et al. (2008), city carbon budgets are needed todevelop a climate policy instrument for local governments.

The standards and methods to quantify emissions from the various citysources will require that both ¹³C and ¹⁴C be measured and integratedwithin the budget analysis framework. Such a framework could consist ofseveral budget allocation methods including:

-   -   1. Allowance allocation via auction,    -   2. Uniform allowance allocation on a per capita basis,    -   3. Using current per capita emissions as a starting point and        transitioning gradually to a uniform allowance allocation on a        per capita basis, and,    -   4. Using current per capita emissions as a starting point and        reducing allowance allocation by the same percent for all        localities.

However, few if any direct measurements have been proposed formanagement or compliance of the emissions, and thus reductions and otheractions based on estimates may be in significant error and be costly.Thus, use of the system of systems would be highly valuable to establishbudgets and verify estimated emissions data for city scale environments.

The system of systems would be placed strategically throughout a cityscale landscape. Data collection for ¹²C, ¹³C, ¹⁴C and other speciessuch as carbon monoxide (CO) would be collected and transmitted asdescribed earlier. Transmitted data would then be used in alreadydeveloped models that incorporate real time meteorological data forwinds, etc. In select locations an eddy covariance tower, alsocommercially available, could be used to augment data and establish fluxpatterns for specific areas of the city. This concept is alsoillustrated in FIG. 32 for the City of NY in one embodiment. The lowerleft panel shows GMP site locations along both shores of Manhattan witha central mid Manhattan site. Other GMP locations are shown to the eastand west of Manhattan for illustration purposes. The GMP apparatus canbe located on top of buildings and above the ground layer ensuring wellmixed air.

One skilled in the art of gas emissions from city sources can readilysee that automotive carbon emissions will have a ¹³C and ¹⁴C isotopicprofile that is distinct and detectable from emissions based on naturalgas and coal. All of the fossil fuel sources will have essentially no¹⁴C rendering a value of −1000 per mil ¹⁴CO₂. However, there issufficient range in isotopic composition in ¹³CO₂ ratios to separate gasfuel (auto fuels) from coal and natural gas as illustrated in FIG. 2. Inaddition, as a measure of the use of bio-based fuels mixing lines from−1000 to modern ¹⁴C could be used (see FIG. 2). Thus, the GMP and systemof systems would be important in detailing carbon budgets. The isotopicdata would be used to construct detailed city wide zones of emissionlevels when coupled with meteorological models, and such data could beused in cases where reductions can be verified to enter trading marketswhere such credits (reduction credits) can be registered and tradedaccordingly (e.g., Regional Greenhouse Gas Initiative, RGGI, 2009).

Example 6 Carbon Sequestration Emissions Trading

Referring to FIG. 34 an example application to carbon sequestration ofpower plant carbon emissions is described. Measuring, monitoring,verification and accounting (MVA) has been identified as one of the mostimportant ways to ensure that carbon capture and storage (CCS) projectsare safe and reliable. Leakage associated with injection wells,inappropriately sealed abandoned wells, or unidentified/poorlycharacterized faults and fractures may result in point, line, or areaCO₂ sources of varying intensity. Reliable measuring and monitoringsystems, with the required sensitivity and resolution, must therefore beavailable for a range of leakage scenarios. Detection andcharacterization of potential CO₂ leakage from CCS sites may bechallenging in the near-surface environment due to the large spatial andtemporal variation in background CO₂ fluxes (e.g., Oldenburg et al.,2003; Lewicki et al., 2005; 2009; Leuning et al., 2008). Also, the areaof a given surface CO₂ leakage signal could be several orders ofmagnitude less than the total area (e.g., ˜100 km²) of the CO₂ reservoirabove which monitoring will be carried out. Consequently, innovative andadvanced monitoring technologies are required with the capability todetect, locate, and quantify CO₂ leakage signals with potentially smallmagnitude and area, relative to background CO₂ variations and the totalarea of investigation, respectively.

As shown in FIG. 2, it is clear that ¹³C ratios cannot distinguishbetween biogenic and fossil fuel sources. Nor can total CO₂concentration data be used to unequivocally identify leakage of fossilfuel derived CO₂ from a carbon capture and storage site. A distinctsignal for fossil fuel can be unequivocally be found in ¹⁴C ratiosalone. However, as can be appreciated in the assessment of leakage froma large scale carbon sequestration project, leakage of stored fossilfuel derived CO₂ in most cases will blend with biogenic CO₂ as itdiffuses through local soils, plants and water bodies. Referring to FIG.34 again, the primary goal of carbon sequestration and capture is toessentially bury CO₂ in gaseous form as it exits from power plants or istransported via pipeline from a central storage facility. Burial cantake place in a wide variety of geological formations on land and underthe sea. However, a central feature of the approach is negligibleleakage after burial and capping of the burial location. In most casesthe potentially affected area is many square miles and thus the systemof systems approach is well suited for this distributed applicationthat:

-   -   1) Provides ¹⁴CO₂ signal for fossil fuel CO₂, ¹³CO₂ signal for        biogenic CO₂ and total ¹²C₂ measured for eddy covariance        (sampling rate 1 to 10 Hz ideally, up to 100 Hz), selected gas        streams, soil gas at the surface and at depth and extracted CO₂        from groundwater.    -   2) Provides for an inter-calibrated network of analyzers to        ensure comparable results for each device. Placement may be        dependent on geological footprint of the injection site and        could range from 1 GMP every square mile to one unit for every        10 to 20 square miles. Locations of analyzers can be placed in        proximity to areas particularly labile to leakage (e.g., well        heads, faults).    -   3) Provides for a telemetry system to transmit data to a central        location.    -   4) Provides for data analysis and model integration.

The GMP analyzers will receive gas from selected areas by sample linesfrom specific sources including well heads 700, 701, 702, soil surfaceflux chambers 710 and 711, buried soil gas collection probes at severaldepths 710, 711, CO₂ extracted from ground water 703, 704, local bodiesof water, down hole monitoring sites, and eddy flux towers in forestedareas 708, 709. According to FIG. 2 the system of systems employing themulti-isotopic analyzer can distinguish pure fossil derived CO₂ gas with¹⁴C ratios from −1000 per mil and pre biogenic derived CO₂ with ¹⁴Cratios of modern (approx. 1 to 50 per mil), as well as blends along themixing line for both end members. The range for ¹³CO₂ is approximately−10 per mil for pure grassland emissions (C4 grasses) to approximately−30 per mil representing typical C3 based CO₂ derived from biomass.Referring to FIG. 34, CO2 leakage can occur along faults 705, 706, 707and thus a variety of detection methods as described above is requiredto detect leakage even at very low rates. For example, a leakage rate of1.0%, 0.1% and 0.01% from a total sequestration of 100,000 tons CO₂ willresult in loss of 1000, 100 and 10 tons per year respectively. Asdescribed previously, sample concentration of ¹⁴CO₂ even at very lowlevels (e.g., sub ppm) can be accomplished utilizing the cryogenic trapprocess and thus provide effective leakage rate determination at verylow levels.

Thus, a combination of approaches described in previous examples (soil,forest, oceanic, agriculture) can be used in combination tounequivocally identify leakage of CO₂ derived from fossil fuel andsubsequently buried. Placement of gas sampling locations may include,without limitation, pipe structure gas flow at well head, down hole orin surface structures, land surface locations including soil surfaceflux, eddy correlation towers and at depth soil sampling of the gas soilprofile.

Example 7 Flue Gas Carbon Emissions Trading

Referring to FIG. 35 an example of measuring and monitoring to establishrelative proportions of biogenic and fossil fuel derived CO₂ from powerplant and other industrial activities is described. Power plantemissions are among the key sources that are currently identified inexisting trading schemes as specified by the Kyoto Protocol and placedinto practice in the EU ETS and other trading groups. However, actualemissions data are not the primary source of information on suchsources, but rather, estimations are used based on the type of fuelburned, combustion efficiencies and other factors pertaining to fuelburn efficiency, rates of fuel consumption, etc. Thus, for the mostvisible and directly quantifiable point sources of CO₂ emissions underregulatory and voluntary programs, actual measurements are not routinelyused to verify budgets and emissions reporting.

In addition, it is increasing clear that the combustion of biogenicmaterials including all types of biofuels creates a key approach toreduce emissions liability since all biofuel usage is credited as“climate-neutral” and therefore not subject to CO₂ emissions regulationsor carbon trading caps. Thus, a reliable and continuous flow method todifferentiate between fossil and biogenic carbon dioxide emissions wouldbe highly valuable to those utilizing biogenic source materials in powerplants and other industrial activities. Currently, either sourcematerial as solid or liquid is subjected to manual ¹⁴C analysis usingtypical scintillation counting or Accelerator Mass Spectrometry (AMD)according to the standard method of ASTM D6866 (Staber et al. 2008;Reddy et al., 2008). The rationale applicable to this approach is wellunderstood and is based on the mixing of end members from pure fossilderived CO₂ and pure biogenic derived CO₂ as illustrated graphically inFIG. 2.

A determination that verifies the blend of biogenic and fossil derivedsource in combustion relies on a direct measurement on the % renewablecontent vs. % fossil content of, for example, gasoline blends regardlessof chemical composition. In doing so, it identifies fuel blendscontaining renewable ethanol vs. synthetic ethanol derived from coal ornatural gas. Thus, a system of systems that samples either flue gas ordirectly combusts liquid fuel blends and subsequently analyzes theresulting CO₂ is valuable. Since renewable ethanol is synthesized frommodern day plants and the gasoline itself is synthesized from fossilpetroleum, a measure on the blend will directly quantify the amount ofrenewable ethanol in that blend. For example, a blend containing 10%renewable ethanol will give a result of 10% renewable content, whereas ablend containing 10% synthetic ethanol will give a result of 0%renewable content, even though in both cases 10% ethanol is present inthe gasoline blend. This characterization supports the underlying intentbehind bio-ethanol use. It also adds protection to domestic stakeholdersin the absence of truly verifiable origin of ethanol. The approachemployed with the system of systems may also be used for verification ofbio-diesel and bio-diesel derived products such as lubricants. As withstationary source combustion, any industrial process that generates CO₂during a combustion process can employ the system of systems to estimatethe carbon-neutral fraction of the total CO₂ emitted.

Some industrial processes that liberate CO₂ include, but are not limitedto aluminum production, ammonia production, cement production, clinkerproduction (including CO₂ emitted from the production of lime), metalproduction, hydrogen production, methanol production, iron and steelproduction, and soda ash production.

Other industrial processes combust waste to generate electricity,liberating CO₂ as a resultant byproduct. A GMP quantifies thecarbon-neutral CO₂ within the facility emissions. Combustion of wastematerial and wastewater sludge are examples of combusted waste.

Examples of Industries that combust waste to produce electricity are thepaper/pulp and medical waste disposal sectors. Crop residue burning isanother agricultural application that can use the GMP for monitoringpurposes. For example, burning of crop residues in the production ofethanol can be measured and monitored with the GMP, providing new sourceof carbon credits. As with stationary source combustion, thecarbon-neutral CO₂ liberated in the combustion process can bedetermined.

The application of a GMP to derive a “Biomass CO₂ content” for carbondioxide effluents is built on some similar concepts to those used by theUS Department of Agriculture to derive the biobased content ofmanufactured products containing biomass carbon. It is done by comparinga relative amount of radiocarbon (¹⁴C) in an unknown sample to that of amodern reference standard. The ratio in contemporary biomass will be100% and the ratio in fossil materials will be zero. Carbon dioxidederived from combustion of a mixture of present day biomass and fossilcarbon will yield a GMP result that directly correlates to the amount ofbiomass carbon combusted and carbon-neutral CO₂ generated.

The GMP can be calibrated against the modern reference standard providedby the National Institute of Standards and Technology (NIST) with adefined radiocarbon content of 100% contemporary carbon for the year AD1950. AD 1950 was chosen since it represented a time prior tothermo-nuclear weapons testing which introduced large amounts of excessradiocarbon into the atmosphere with each explosion (termed “bombcarbon”). This was a logical point in time to use as a reference sincethis excess bomb carbon would change with increased or decreased weaponstesting. In certain embodiments, fixed correction for this effect wouldbe applied per the GMP applications, applying specifically to carbonremoved from the atmospheric CO₂ reservoir since about 1996.

GMP results relate directly to the percentage carbon-neutral CO₂ in anincineration effluent. A value of 71% renewable content measured on CO₂effluent would indicate that 71% of the exhausted CO₂ was from biomass(29% from fossil fuel). It does not represent the weight of biomasscombusted or the weight of fossil fuel combusted. This is advantageoussince the weight of the fuels only indirectly relate to the up-take ofcarbon dioxide from the atmosphere. The respiration uptake compound wascarbon dioxide and the combustion effluent was carbon dioxide. The GMPresult will directly and specifically relate to the amount ofbiogenic/carbon-neutral CO₂ consumed and expelled.

Here we illustrate a specific example of the application referring toFIG. 35. A volume/volume blend percentage of biodiesel in a realisticfuel mixture can be estimated based on its ¹⁴C content, as follows.First, the carbon of the fuel blend with respect to the modern(biological) component and fossil (petrodiesel) component are used towrite a Δ¹⁴C mass balance:

Δ¹⁴C_(mixture)=FC,_(bio)Δ¹⁴C_(bio)+(1-FC,_(bio))Δ¹⁴C_(petro)   (eq 1)

where Δ¹⁴C_(mixture) is the measured ¹⁴C content of the biodiesel blendvia traditional or AMS radiocarbon determination. The Δ¹⁴C_(bio) can betaken as an average measured value of several typical retail fat and oilsources used in biodiesel preparations—in this case we take a value of62±7‰ consistent with reported values for modern corn in North America(the primary feedstock for cattle) showing an average range of 55 to66‰, collected in 2004 (Huseh et al., 2007).

The Δ¹⁴C_(petro) was fixed at a value −1000‰, consistent withmeasurements of petroleum end members as well known to those skilled inthe art of radiocarbon determinations of fossil fuel components and asreported in FIG. 2. Additionally, FC,_(bio) is the mass fraction of thetotal mixture carbon that is derived from biological components.

Thus, rearranging (eq 1), FC,_(bio) can be expressed as:

FC,_(bio)=Δ¹⁴C_(mixture)−Δ¹⁴C_(petro)/Δ¹⁴C_(bio)−Δ¹⁴C_(petro)   (eq 2)

Equation 2 shows that the proportion of biological carbon in the samplefuel blend (FC,_(bio)) can be easily determined based on the measuredΔ¹⁴C_(mixture) of the sample and the a priori known Δ¹⁴C_(bio) andΔ¹⁴C_(petro) values of the end member materials. We assumed thatΔ¹⁴C_(petro) (−1000‰) and Δ¹⁴C_(bio) (62+−7‰) represent reasonablyconstant end members, such that variation in FC,_(bio) is fullyexplained by the measured Δ¹⁴C_(mixture) value.

In practice, however, a slight complication may arise in that taking aspecific example of B100 biodiesel production the United States andEurope, the transesterification step from fats to fatty acid methylesters (FAMEs—the common mixture for biodiesel) utilizes fossilmethanol. For example, for a C18 FAME, 18/19 of the carbon (fatty chain)is from fats and oils and the other 1/19 (methyl carbon) ispetroleum-derived. Thus, in order to relate FC,bio more precisely to theB100 end member one can define the following equation:

FC,_(B100)=FC,_(bio)/RC,_(bio/B100)   (eq 3)

where FC,_(B100) is the mass fraction of B100 carbon in the biodieselblend, and RC,_(bio/B100) is the ratio of biological carbon to totalcarbon in the pure component B100. Thus, the blend percentage (v/v) ofB100 (B*) in a fuel blend may be calculated as follows:

B*=100[V_(B100)/V_(B100)+V_(petro)]  (eq 4)

where V_(B100) and V_(petro) are the extensive volumes of the biologicaland petroleum-based components, respectively, in a control volume offuel blend. The individual component volumes can then be expressed as:

Vx=[mC,x+mH,x+mO,x/Fx]  (eq 5a)

which equates to:

mC,x/Fx [1+mH,x/mC,x+mO,x/mC,x)   (5b)

where mC,x, mH,x, and mO,x are the total masses of carbon, hydrogen, andoxygen, respectively, for component x in the blend control volume, andFx is the density of component x.

For notation simplicity, one can write:

θC,_(B100)=(1+mH,_(B100) /mC,_(B100) +mO,_(B100) /mC,_(B100))   (eq 6)

and,

θC,_(petro)=(1+mH,_(petro) /mC,_(petro))  (eq 7)

where θC,_(B100) and θC,_(petro) characterize the mass abundances ofhydrogen and oxygen relative to carbon in the biological andpetroleum-based components, respectively. Combining eqs 4-7 andrearranging, the calculated v/v blend percentage of a biodiesel, B*, canbe rewritten as:

B*=100/[1(F_(B100)/F_(petro))(θC,_(petro)/θC,_(B100))(mC,_(petro)/mC,_(B100))   (eq 8)

Now recognizing that

mC,_(petro) /mC,_(B100)=(RC,_(bio/B100)/FC,_(bio)−1),

(eq 8) can be expressed as

B*=100/[1+(F_(B100)/F_(petro))(θC,_(petro)/θC,_(B100))(RC,_(bio/B100)/FC,_(bio)−1)]  (eq9)

where F_(B100), F_(petro), θC,_(B100), θC,_(petro), and RC,_(bio/B100)are properties of the two pure component liquids (B100 and petrodiesel),and thus FC,_(bio) controls the calculated blend content, B*. One canparameterize F_(B100), F_(petro), θC,_(B100), θC,_(petro), andRC,_(bio/B100) using the averaged values calculated from a datacompilation of retail B100 and petrodiesel products, based on literaturesurveys (e.g., Reddy et al., 2008). Hence (eq 9) does not requirecalibration to a designated normative fuel blend; rather, it can beparameterized with pure-component properties that are relatively stablefor a wide range of source materials. Thus, (eq 9) can accuratelyestimate the biodiesel content of any realistic fuel blend based simplyon the measured FC,_(bio) value (eq 2).

A further simplification can be made by parameterizing (eq 9) usingsimple averages of F_(B100), F_(petro), θC,_(B100), θC,_(petro), andRC,_(bio/B100) property values from a broad range of retail petrodieselsand B100's published in the open literature (Reddy et al., 2008).Employing such input parameters, (eq 9) is further simplified to:

B*=100/[(0.869/FC,_(bio))+0.0813]  (eq 10)

where the lumped parameters, 0.869 and 0.0813, are dimensionless. Forclarity, the notation “B*” is used to indicate calculated blend content.

Thus, in the example illustrated in FIG. 35, a GMP 800 is installed toreceive stack flue gas resulting from a mixture of petro diesel andbiogenic carbon via a combustion chamber 802 with a petro dieselcomponent of ¹⁴C of −1000‰ 803 and a biogenic component consisting oftypical restaurant French fry fat of +59‰ 804 the blend 805, or B* canbe computed to equal according to the equations above to 19.4%±0.6%(Reddy et al., 2008). The data so obtained combined with volumetric flowmeasurements also made at the stack will result in the total amount offossil and biogenic carbon released to the atmosphere. For the sake ofillustration, we assume that 80 metric tons of fossil and 20 metric tonsof biogenic carbon dioxide were released. Thus, the designation of theemissions so calculated over time for one plant or over a definedspatial scale would be rendered as:

+¹⁴C units: 80 metric tons.

+¹³C units: 20 metric tons.

Any group of power plants by region or by company may be so combined ina GMP network to provide a continuous and accurate record of non-fossilsource carbon to the combustion process. The GMP in this usage will be adeterrent to fraud as power production sites that mix fuels of biogenicand fossil could report data with a bias towards the non-fossil.

Pricing may be applied accordingly in relation to market exchangeconditions and other factors.

Thus, the system of systems apparatus as described above in conjunctionwith well known methods practiced in the literature can be used toeffectively measure, monitor, report, aggregate and monetize based onisotopic constraints units of carbon to be used in market based systemsfor greenhouse exchanges, regulatory or compliance frameworks or forvoluntary emissions reductions, budgets, and policy makers.

Example 8 A Global Radiocarbon Budget and the Nuclear Fuel Cycle

A consequence of the widespread deployment of GMPs offering high datarate and high precision for ¹⁴CO₂ is a refinement of the globalradiocarbon budget itself. Such a budget has applications in themonitoring of nuclear power production offering the potential ofgenerating a global nuclear fuel cycle and the detection of roguenuclear power plants. This follows from the well know reactions thattake place during operation of nuclear power plants and fuelreprocessing (Yim and Caron 2006) that releases the radionuclides oftritium and ¹⁴CO₂. While the pulse of ¹⁴C after the bomb pulse is wellknown (e.g., Broecker 200) the background ¹⁴C is now near natural levels(Broecker 2007) and the production of ¹⁴C due to nuclear reactors isestimated to be about 0.3% of natural levels (Park et al., 2008). Thus,the addition of ¹⁴C from nuclear reactors in the areas in which suchreactors operate can be used to characterize processing activities ofsuch plants. Carbon-14 is present in virtually all parts of the nuclearreactor primary system and has a high production rate. It is released tothe environment through gaseous and liquid discharges and though thedisposal of solid radioactive waste. Any nuclear power activity willemit ¹⁴CO₂ as it is difficult to directly contain (e.g., Yim and Caron2006). In areas where no such nuclear power plants exist the detectionof ¹⁴C above background levels should be possible within the 2 per milrange of the current detection capability of the GMP and with anensemble of GMPs covering the area. ¹⁴C values of plant material up to123 per mil have been reported by Roussel-Debet et al. (2006) in thevicinity of a nuclear power plant over a period of 10 years suggestingfeasible detection of ¹⁴CO₂ during periods of reactor activity. Underideal conditions a nuclear power plant operating without authorityshould be readily identified. The stripping of CO₂ from groundwater andsubsequent analysis for ¹⁴CO₂ by the GMP also allows the specific routeof detection by ebullition of gaseous emissions from underwater sourcesor from discharge streams from such facilities.

While a number of radionuclides and analyses are conducted forsurveillance of nuclear power activity and for verification of treatyprovisions (e.g., Gitzinger et al., 2007), they require close proximityto the source of approximately 25 meters, depending on number ofdetectors and/or area of detector, for both gamma ray and neutronemitting materials (Kallman 2008). The production and emission of ¹⁴CO₂released from nuclear power production is not well known but has beenestimated for the worlds reactors (e.g., Davis 1977; Yim and Caron2006). A number of studies have sampled for ¹⁴C in plant sample fromareas surrounding nuclear reactors (e.g., Korashi et al., 2006; Dias, C.M., et al., 2008) and have provided background levels due to release of¹⁴CO₂ from a variety of reactor types including boiling water reactorsand pressurized water reactors (Yim and Caron 2006). However, actualmeasurements of ¹⁴CO₂ as gaseous CO₂ are lacking. Thus, a system ofsystem as disclosed herein constitutes a feasible approach to measuringand monitoring one of the major emissions from nuclear power plants,¹⁴CO₂, that will increase as the use of nuclear power is more widelyadopted.

A system of systems will:

-   -   1) Provide ¹⁴CO₂ signal for fossil fuel CO₂, ¹³CO₂ signal for        biogenic CO₂ and total ¹²CO₂ measured for eddy covariance        (sampling rate 1 to 10 Hz ideally, but up to 100 Hz), selected        gas streams, soil gas at the surface and at depth and extracted        CO₂ from groundwater.    -   2) Provide for an inter-calibrated network of analyzers to        ensure comparable results for each device. GMP density and        arrangement will depend upon local conditions but be such that        the source signal for eddy covariance is detected within the        range of +2 to +200 per mil, taking background 14C as        approximately 5 to 10 per mil.    -   3) Provide for a telemetry system to transmit data to a central        location.    -   4) Provide for data analysis and model integration.

The use of a system of systems to quantify ¹⁴CO₂ could be applied tomeasuring, monitoring, verification and accounting for nuclear powerfacilities in much the same manner as the system of systems would beused for carbon capture and storage. A variety of eddy covariance,groundwater CO₂ sampling, point locations (e.g., different parts of thereactor infrastructure) and soil CO₂ sampling sites could be situatednear nuclear installations. The specific arrangement and configurationof the GMPs would depend on the source strength of the power plantsignal, proximity allowed to a given facility and other factors. Theneed for a system of systems is recognized by the approach taken insampling large areas of a given region versus traditional radionuclideanalyses that depend on direct access to plant sample locations. Thesystem of systems may be a relatively inexpensive route compared toanti-neutrino detection that while offering potentially far-fieldmonitoring is estimated to cost several trillion dollars (e.g., Guillian2006).

The following references are cited herein and incorporated by referenceherein in their entireties

US 2008/0015976 Jan. 17, 2008

U.S. Pat. No. 6,164,129 Dec. 26, 2000

US 2007/0250329 Oct. 25, 2007

US 2007/0224085 Sep. 27, 2007

US 2008/0228632 Sep. 18, 2008

US 2008/0228665 Sep. 18, 2008

US 2008/0228630 Sep. 18, 2008

US 2008/0228628 Sep. 18, 2008

US 2008/0221750, Sep. 11, 2008

US 2008/0015975 Jan. 17, 2008

US 2008/0015976 Jan. 17, 2008

US 2008/0059206 Mar. 6, 2008

U.S. Pat. No. 7,154,595 Dec. 26, 2006

U.S. Pat. No. 5,394,236

U.S. Pat. No. 5,783,445

U.S. Pat. No. 5,818,580

U.S. Pat. No. 5,864,398

WO 99/42814

U.S. Pat. No. 7,616,305

Air Resources Board, State of California. ARB 2009http://www.arb.ca.gov/cc/factsheets/ab32factsheet.pdf (2009).

Allison, C. E., Francey R. J., and Steele, L. P. The InternationalAtomic Energy Agency circulation of laboratory air standards for stableisotope comparisons: aims, preparation and preliminary results. In:Isotope aided studies of atmospheric carbon dioxide and other greenhousegases Phase II (IAEA-TEDOC-1269). IAEA, Vienna, Austria, pp 5-23 (2002).

Allison C. E., Francey R. J., White J. W. C, Vaughn B. H., Wahlen M.,Bollenbacher A., Nakazawa T. What have we learnt about stable isotopemeasurements from the IAEA CLASSIC? In: Report of the eleventh WMO/IAEAmeeting of experts on carbon dioxide concentration and related tracermeasurement techniques, Tokyo, Japan, 25-28 Sep. 2001, MO/GAW Report No.148, Geneva, pp 17-30 (2003).

Amico di Meane, E., Plassa, M., Rolle, F., Sega, M. Metrologicaltraceability in gas analysis at I.N.Ri.M: gravimetric primary gasmixtures. Accred Qual Assur 14:607-611 (2009).

Amundson, R., Sanderman, J., and Yoo, K. Environmental and geologicalcontrols on the soil carbon cycle in a changing world (in GeologicalSociety of America, 2008 annual meeting, Anonymous,) Abstracts withPrograms—Geological Society of America (October, vol. 40(6):24 (2008).

ASTM D6866-08. Active Standard: D6866-08. Standard Test Methods forDetermining the Biobased Content of Solid, Liquid, and Gaseous SamplesUsing Radiocarbon Analysis. ASTM (2008).

Barford, C., Steven C. Wofsy, Michael L. Goulden, J. William Munger,Elizabeth Hammond Pyle, Shawn P. Urbanski, Lucy Hutyra, Scott R.Saleska, David Fitzjarrald, and Kathleen Moore. Science 294: 1688-1691[DOI: 10.1126/science.1062962 (2001).

Becker, J. F., Sauke, T. B., Loewenstein, M. Appl. Opt. 31: 1921 (1992).

Bonan, G. B. A land surface model (LSM version 1.0) for ecological,hydrological, and atmospheric studies: Technical description and user'sguide, 150 pp., Natl. Cent. for Atmos. Res., Boulder, Colo. (1996).

Bradley, L. C., Soohoo, K. L., Freed, C. Absolute frequencies of lasingtransitions in nine CO2 isotopic species. IEEE Journal of QuantumElectronics vol. QE-22, No. 2 (1986).

Broecker, W. Radiocarbon. In: Treatise on Geochemistry, Elsevier 2007.

Brown, M. A., Levine' M. D., Short, W., Koomey. J. G., Energy Policy29(14): 1179-1196 (2001).

Canadell, J., Quere C., Raupach M., Field C., Buitenhuis E., Ciais P.,Conway T., Gillett N., Houghton R., Marland G. Contributions toaccelerating atmospheric CO2 growth from economic activity, carbonintensity and efficiency of natural sinks PNAS early edition, 10.1073(2007).

Capoor, K., and Ambrosi. 2007. State and Trends of The Carbon Market2007. World Institute, Washington, DC, 2007.

Chicago Climate Exchange 2010.http://www.chicagoclimatex.com/content.jsf?id=781.

Ciais P., and four others. A Large northern hemisphere terrestrial CO2sink indicated by the 13C/12C ratio of atmospheric CO2. Science269(5227): 1098-1102 (1995).

Convery F. J. and Redmond, L. Market and Price Developments in theEuropean Union Emissions Trading Scheme. Rev Environ Econ Policy 1:88-111 (2007).

Coplen, T. B. New manuscript guidelines for the reporting of stablehydrogen, carbon, and oxygen isotope-ratio data. Geothermics24(5-6):707-712 (1995).

Coplen T. B. et al., and five others. New Guidelines for delta ¹³Cmeasurements. Anal. Chem. 78: 2439-2441 (2006).

Davis, W. Carbon-14 production in nuclear reactors. ORNL/NUREG/TM-12(1977).

Dias, C. M. and 4 others. 14C content in vegetation in the vicinities ofBrazilian nuclear power reactors. J. Env. Radio. 99(7): 1095-1101(2008).

European Union Emissions Trading Scheme. www.euets.com. 2009.

Ellerman, D. A. and Joskow, P. L. The European Union's Emissions TradingSystem in Perspective. MIT, May 2008.

Flesch, T. K., Wilson, J. D., Harper, L. A., Crenna, B. P., Sharpe, R.R. Deducing ground-to-air emissions from observed trace gasconcentrations: a field trial. J. Appl. Meteorol. 43, 487-502 (2004).

FLUXNET. http://www.fluxnet.ornl.gov/fluxnet/index.cfm.

Freed, C. Ultrastable CO2 Lasers. The Lincoln Laboratory Journal. Vol.3(3): 479-500 (1990).

Freed C. CO2 Isotope Lasers and their applications in tunable laserspectroscopy. Chapter 4, pp. 63-165 in “Tunable Lasers Handbook”(Academic Press, 1995, F. J. Duarte, Editor).

Friedmann, S. J, Geological Carbon Dioxide Sequestration Elements vol.3, pp 179-184, (2007).

Gitzinger C. and 3 others. Technical Report: Verifications under theterms of article 35 of the euratom treaty. Finnish National MonitoringNetwork for Environmental Radioactivity. FI-07/02 (2007).

Global view. NOAA. http://www.esrl.noaa.gov/gmd/ccgg/globalview/(2010).

Graven, H. D. and 5 others. Vertical profiles of biospheric and fossilfuel-derived CO2 and fossil fuel CO2: CO ratios from airbornemeasurements of delta 14C, CO2 and CO above Colorado, USA. Tellus 61B,536-546 (2009).

Grell, G., Dudhia, J., and Stauffer, D. A description of thefifth-generation Penn State/NCAR mesoscale model (MM5), Natl. Cent. ForAtmos. Res., Boulder, Colo. (1995).

Guillian, E. H. Far field monitoring of rogue nuclear activity with anarray of large anti-neutrino detectors. Earth, Moon, and Planets 99:309-330 (2006).

Gulden, M. L., et al., and 4 others. Measurements of carbonsequestration by long-term eddy covariance: methods and a criticalevaluation of accuracy. Global Change Biology 2: 169-182 (1996).

Ha-Duong, M., and Loisel R. Zero is the only acceptable leakage rate forgeologically stored CO2: an editorial comment Climatic Change 93:311-317(2009).

Hamalainen, K M; Jungner, H; Antson, O; Rasanen, J; Tormonen, K; Roine,J. Penn State/NCAR mesoscale model (MM5), Natl. Cent. For Atmos. Res.,Boulder, Measurement of Biocarbon in Flue Gases Using 14C Radiocarbon,Vol 49(2): 325-330 (2007).

Hamilton, K., Sjardin, M., Marcello, M., and Xu, G. Forging a Frontier:State of the Voluntary Carbon Markets 2008. A report by EcosystemMarketplace & New Carbon Finance, May 2008.

Heimann, M. and Maier-Reimer, E. On the relations between the oceanicuptake of carbon dioxide and its carbon isotopes. Global BiogeochemicalCycles, 10: 89-110 (1996).

Hsueh, D. Y., and 6 others. Regional patterns of radiocarbon and fossilfuel-derived CO2 in surface air across North America. Geophys. Res.Lttrs. VOL. 34, L02816, doi:10.1029/2006GL027032 (2007).

Humphries, S. D., A. R. Nehrir, C. J. Keith, K. S. Repasky, L. M.Dobeck, J. L. Carlsten, and L. H. Spangler, “Testing carbonsequestration site monitor instruments using a controlled carbon dioxiderelease facility,” Appl. Opt. 47, 548-555 (2008).

Hurley, P. J., Physick, W. L., Luhar, A. K. TAPM: a practical approachto prognostic meteorological and air pollution modeling. Environ. Model.Software 20, 737-752 (2005).

Galik, S. C., Mobley, M. L., Richter, D. A virtual “field test” offorest management carbon offset protocols: in influence of accounting.Mitig. Adapt Strage Glob Change 14:677-690 (2009).

IPCC. Contribution of Working Group Ito the Fourth Assessment Report ofthe IPCC (ISBN 978 0521 88009-1) (2007).

IPCC. Climate Change 2007 and 2008—The Physical Science Basis (2008).

Kallman, C. T. Detection technology in the 21^(st) century: the case ofnuclear weapons of mass destruction. US Army War College, Carlisle, Pa.(2008).

Keeling, C. D. The concentration and isotopic abundances of atmosphericcarbon dioxide in rural areas. Geochem. et Cosmochem. Acta 13 (322-334)(1958).

Keeling, C. D. The Suess effect: 13Carbon-14Carbon interrelations.Environment International Vol. 2: 229-300 (1979).

Korashi, J. and 4 others. A simple and reliable monitoring system for 3Hand 14C in radioactive airborne effluent. J. Radio. Nuc. Chem. 268(3):475-479 (2006).

Kosovic, B. Monache, L. D., Cameron-Smith, P., Bergman, D., Grant, K.,Guilderson, T. Toward regional fossil fuel CO2 emissions verificationusing WRF-CHEM. 9^(th) WRF users workshop, Boulder, Colo. Jun. 26, 2008.

Lai, C. T., Schauer, A. J., Owensby, C., Ham, J. M., Helliker, B., Tans,P. P., Ehleringer, J. R. Regional CO2 fluxes inferred from mixing ratiomeasurements: estimates from flask air samples in central Kansas, USA.Tellus Vol. 58b, pp. 523-536 (2006).

Leuning, R., Etheridge, D., Luhar, A., Dunse, B. Atmospheric monitoringand verification technologies for CO₂ geosequestration. Intl J.Greenhouse Gas Controls 2: 401-414 (2008).

Levin, I., J. Schuchard, B. Kormer, K. O. Munnich. The continentalEuropean Sues effect. Radiocarbon 31:431-440 (1989).

Levin, I., R., Graul, N. B. A. Trivett. Long term observations ofatmospheric CO2 and carbon isotopes at continental sites in Germany.Tellus 47B:23-34 (1995).

Levin, I., Kormer, B., Schmidt, M., Sartorius, H., A novel approach forindependent budgeting of fossil fuel CO2 over Europe by 14CO2observations. Geo. Res. Letters Vol. 30 (23), 2194 (2003).

Levin, I., Rodenbeck, C. Can the envisaged reductions of fossil fuel CO2emissions be detected by atmospheric observations? Naturwissenschaften95: 203-208 (2008).

Lewicki, J. L., G. E. Hilley, M. L. Fischer, L. Pan, C. M. Oldenburg, L.Dobeck, and L. Spangler, Eddy covariance observations of surface leakageduring shallow subsurface CO2 releases, Journal of GeophysicalResearch—Atmospheres, 114, D12302 (2009).

Libby W. F., Anderson E. C., and Arnold J. R. Age determination byradiocarbon content: worldwide assay of natural radiocarbon. Science109, 227-228 (1949).

Lloyd, J. and 12 others. Vertical profiles, boundary layers, andregional flux estimates for CO2 and its 13C/12C ratio for water vaporabove a forest/bog mosaic in central Siberia. Global BiogeochemicalCycles, 15(2): 267-284 (2001).

Matsumoto, K., and 30 others. Evaluation of ocean carbon cycle modelswith data-based metrics. Geophys. Res. Lett. 31, L07303, doi:10.1029/2003GL018970 (2003).

McNichol, A. P. and 3 others. The rapid preparation of seawater totalCO2 for radiocarbon analysis at the national ocean sciences AMSfacility. Radiocarbon 36(2): 237-246 (1994).

Midwest Greenhouse Gas Accord. www.midwesternaccord.org. 2009.

Murnick, D. E., and Peer, J. Science 263: 945-947 (1994).

Murnick, D., Dogru, O., Ilkmen E. Nuclear Instruments and Methods inPhysics Research B 259 786-789 (2007).

Murnick, D. E., Dogru, O., and Ilkmen, E. Intracavity optogalvanicspectroscopy: An analytical technique for 14C analysis with subattamolesensitivity. Analytical chemistry 80(13):4820-4824 (2008).

Murnick, D. E., Dogru, O, Ilkman, E. Laser based ¹⁴C counting, analternative to AMS in biological studies. Nuclear Instruments andMethods in Physics Research Section B: Beam Interactions with Materialsand Atoms Volume 259(1): 786-789 (2009).

Oldenburg, C. M., Lewicki, L. L., and Hepple, R. P. Near-surfacemonitoring strategies for geologic carbon dioxide storage verification.Earth Science Division, Ernesto Orlando LBNL, ReportLBNL-54089, pp. 1-54(2003).

O'Leary, M. H. Carbon isotopes in photosynthesis. BioScience, 38,328-336 (1988).

Pacala S. W. Letter Reporting on the Orbiting Carbon Observatory.Committee on Methods for Estimating Greenhouse Gas Emissions; NationalResearch Council (2009).

Park, J. H. and 6 others. Isotopic fractionation during pretreatment foraccelerator mass spectrometer measurement of (D3C)2O containing 14Cproduced bhy nuclear reaction. J. Radio. Nuc. Chem. 275(3): 627-631(2008).

Parton, W., and 10 others. Observations and modeling of biomass and soilorganic matter dynamics for the grassland biome worldwide. Glob.Biogeochem. Cycles 7:109-131 (1993).

Peters, W. and 15 others. An atmospheric perspective on North Americancarbon dioxide exchange: Carbon Tracker. Proc. Natl. Acad. Sci. USA, 48,18925-18930 (2007).

Randerson J. T., and 4 others. Seasonal and latitudinal variability oftroposphere delta 14CO2: Post bomb Contributions from fossil fuels,oceans, the stratosphere, and the terrestrial biosphere. GlobalBiogeochemical Cycles, vol 16(4): 1112 (2002).

Raupach, M., Marland G., Ciais P., Quere C., Canadell J., Klepper G.,Field C. Global and regional drivers of accelerating CO2 emissions.PNAS, 104(24):10288-10293 (2007).

Reddy, C. M., Demello, J. A., Carmicheal, C. A., Peacock, E. E., Xu, L.Arey, S. J. Determination of biodiesel blending percentages usingnatural abundance radiocarbon analysis: testing the accuracy of retailbiodiesel blends. Environ. Sci. Technol. 42, pp. 2476-2484 (2008).

Regional Greenhouse Gas Initiative. www.RGGI.og. 2009.

Riley W. and 7 others. 2008: Where do fossil fuel carbon dioxideemissions from California go? An analysis based on radiocarbonobservations and an atmospheric transport model. Journal GeophysicalResearch. VOL. 113, G04002, doi:10.1029/2007JG000625 (2007).

Roussel-Debet, S. and 4 others. Distribution of carbon 14 in theterrestrial environment close to French nuclear power plants. J. Env.Radioactivity 87(3): 246-259 (2006).

Rozanski, K. 1991. International Atomic Energy Agency Consultants' GroupMeeting on C-14 Reference Materials for Radiocarbon Laboratories, Feb.18-20, 1991. Report by K. Rozanski, Section of Isotope Hydrology, IAEA,Vienna (1991).

Saleska, S. R., Shorter, J. H., Herndon, S., Jimenez, R., McMannus, J.B., Munger, J. W., Nelson, D. D., Zahniser, M. S. What are theinstrumentation requirements for measuring the isotopic composition ofnet ecosystem exchange of CO2 using eddy covariance methods? Isotopes inEnv. Health Studies Vol. 42(2), pp. 115-133 (2006).

Salon, D., Sperling D., Meier, A., Murphy, S., Gorham, G., Barrett, J.City carbon budgets: Aligning incentives for climate-friendlycommunities. Institute of Transportation Studies, University ofCalifornia, Davis, Research Report UCD-ITS-RR-08-17 (2008).

Schlesinger, W. H. Carbon sequestration in soils: some cautions amidstoptimism. Agriculture, Ecosystems and Environment Vol. 82: (1-3) 121-127(2000).

Scott, N. A., and 6 others. Changes in carbon storage and net carbonexchange one year after an initial shelterwood harvest at HowlandForest, Me., Environmental management 33(1): S9-S22 (2004).

Scott, M. E. et al., and 11 others. Future needs and requirements forAMS 14 C standards and reference materials. Nuclear Instruments andMethods in Physics Research B 223-224: 382-387 (2004).

Staber, S., Flamme S., Fellner J., Methods for determining the biomasscontent of waste. Waste Management and Research 26: 78-87 (2008).

Steffen W., et al. The Terrestrial Carbon Cycle: Implications for theKyoto Protocol. Science 280: 1393-1394 (1998).

Stork, A., Witte, R., and Fuhr, F. 14CO2 measurement in air: literaturereview and a new sensitive method. Env. Sci. and Technology 31(4) 1997.

Stuiver, M.,and Polach, H. A. Discussion: Reporting of 14C data.Radiocarbon 19(3):355-363 (1977).

Tans, P. P., P. S. Bakwin, and D. W. Guenther. A feasible global carboncycle observing system: a plan to decipher today's carbon cycle based onobservations. Global Change Biology 2:309-318 (1996).

Turnbull J. C., and 5 others. Comparison of 14CO2, CO and SF6 as tracersfor recently added fossil fuel CO2 in the atmosphere and implicationsfor biological CO2 exchange. Geophysical Research Letters, vol 33,L01817 (2006).

Turnbull, J. C. et al., A new High resolution 14CO2 time series forNorth American continential air. J. Geophysical Research Res. 112, D1130(2007).

Tuniz, C. Accelerator Mass Spectrometry. Radiation Physics and Chemistryvol. 61(3-6): 317-322 (2001).

Tuzson, B. and 5 others. QCLAS. A compact isotopologue specific analyzerfor atmospheric CO2. Geophysical Res. Abstracts 10 (EGU2008-A-07132(2008).

Uchida, M., and 9 others. Ecosystem-scale carbon isotope ratios ofrespired CO2 in cool-temperate deciduous forests under Asian monsoonclimate. Journal of Geophysical Research vol. 113. G02015 (2008).

UNFCCC: http://unfccc.int/methods_science/redd/items/4531.php (2008).

Updegraff, K., Zimerman, P. R., Price, M., Capehart, W. J. C-Lock: Anonline system to standardize the estimation of agricultural carbonsequestration credits. Fuel Processing Technology 86:1695-1704 (2005).

Urbanski, S. and 8 others. Factors controlling CO2 exchange ontimescales from hourly to decadal at Harvard Forest. J. Geophys. Res.112, G02020, doi:10.1029/2006JG000293 (2007).

US Climate Change Science Program 2007. Synthesis and Assessment Product2.2: The First State of the Carbon Cycle Report (2007).

Venteris, E. R. and 8 others. A new digital geologic model for carbonsequestration planning in the Appalachian and Michigan basins.Geological Society of America, Abstracts with programs, Vol. 38(4): 14(2006).

West, T. O., and Marland, G. Net carbon flux from agriculturalecosystems: methodology for full carbon cycle analyses. Environ. Pollut.116(3): 439-44 (2002).

Western Climate Initiative. www.westernclimateinitiative.org. 2009.

Werner, A, Brand, W. Referencing strategies and techniques in stableisotope ratio analysis. Rapid Communications in Mass Spectrometry 15:501-519 (2001).

Widory, D. Combustibles, fuels and their combustion products: a viewthrough carbon isotopes. Combustion Theory and Modelling Vol 10 (5) pp.831-841 (2006).

World Meteorological Organization . Global Atmosphere Watch Report, ed.Miller, J. B. (World Meteorological Organization, Geneva), no. 168(2007).

Yim, M, and Caron, F. Life cycle and management of carbonl4 from nuclearpower generation. Progress in Nuclear Energy 48: 2-36 (2006).

Zobitz, J. M., and 5 others. Integration of process-based soilrespiration models with whole ecosystem CO2 measurements. Ecosystems11:629-642 (2008).

Zoe, L., and 6 others. Testing Lagrangian atmospheric dispersionmodelling to monitor CO₂ and CH₄ leakage from geosequestration.Atmospheric Environment 43: 2602-2611 (2009).

Zoe” Loh, Ray Leuning, Steve Zegelin, David Etheridge, Mei Bai, TravisNaylor, David Griffith, Masarie, K. A., Langenfelds, R. L., Allison, C.E., Conway, T. J., Dlugokemcky, E. J., Francey, R. J., Novelli, P. C.,Steele, L. P., Tans, P. P., Vaughn, B., White, J. W. C. NOAA/CSIRO flaskair intercomparison experiment: a strategy for directly assessingconsistency among atmospheric measurements made by independentlaboratories. J. Geo. Res. Vol. 186 (D17), pp., 20445-20464 (2001).

Zwaan B., and Gerlagh R. Effectiveness of CCS with time-dependent CO2leakage. Energy Procedia 1: 4977-4984 (2009).

It will be understood that other embodiments could be created withvariations in function, method and implementation, and variousmodifications can be made without departing from the invention.Accordingly, the scope of the invention should be determined by theappended claims and not limited to the above-described illustrativeembodiments.

1. A system of systems for generating tradable products that separatelyquantify biogenic and fossil carbon in forest air, comprising: (a) acarbon data collection system for collecting carbon flux data in aforest comprising an array of analyzers placed in predeterminedrepresentative locations throughout a forest, wherein each analyzercomprises a ¹²C laser device, a ¹³C laser device, a ¹⁴C laser device, asample chamber to measure the individual amounts of ¹²C, ¹³C, and ¹⁴Cisotopes contained in a forest air sample, and a timer to allowmeasurements of ¹²C, ¹³C, and ¹⁴C isotopes at a rate of at least 1 Hz; astandard reference gas module for obtaining a standard referencebaseline and calibrating the measured amounts of the ¹²C, ¹³C, and ¹⁴Cisotopes from each of said analyzers based on said standard referencebaseline; and a telemetry device for sending measured amounts of ¹²C,¹³C, and ¹⁴C isotopes in the forest air to a data processing system; and(b) a data processing system for converting the measured amounts of ¹²C,¹³C, and ¹⁴C isotopes to tradable products that separately quantifybiogenic and fossil carbon in the forest.
 2. The system of systems ofclaim 1, wherein each analyzer comprises a standard reference gasmodule.
 3. The system of systems of claim 1, further comprising a globalreference system including a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, and a global reference sample cell to measure theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a globalreference sample, and a calibration system for standardizing themeasured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of saiddata collection system based on said measured amounts of ¹²C, ¹³C, and¹⁴C isotopes contained in the global reference sample.
 4. The system ofsystems of claim 3, wherein said global reference system is located in asatellite.
 5. The system of systems of claim 1, wherein said array ofanalyzers comprises more than 25 analyzers.
 6. The system of systems ofclaim 1, wherein said array of analyzers comprises more than 100analyzers.
 7. The system of systems of claim 1, wherein said timerallows measurements of ¹²C, ¹³C, and ¹⁴C isotopes at a rate up to 100Hz.
 8. The system of systems of claim 1, wherein said predeterminedrepresentative locations include borders of discrete forest areas,wherein said borders include a region, a state, a group of states, aborder configuration defining a greenhouse gas treaty or otherconvention that requires monitoring greenhouse gases.
 9. The system ofsystems of claim 1, wherein said predetermined representative locationsinclude above the forest canopy, below the forest canopy and at theforest floor.
 10. The system of systems of claim 1, wherein said dataprocessing system comprises one or more conversion systems parameterizedfor biogenic and fossil fuel carbon to convert the measured amounts of¹²C, ¹³C, and ¹⁴C isotopes in the data processing system to tradableproducts that separately quantify biogenic and fossil carbon in theforest.
 11. A method for generating tradable products that separatelyquantify biogenic and fossil carbon in forest air, comprising: (a)placing an array of analyzers at predetermined representative locationsthroughout a forest, wherein each analyzer comprises a ¹²C laser device,a ¹³C laser device, a ¹⁴C laser device, and a sample chamber; (b)collecting forest air samples in the sample chambers of the analyzersand measuring the individual amounts of ¹²C, ¹³C, and ¹⁴C isotopescontained in the samples at a rate of at least 1 Hz; (c) obtaining astandard reference baseline with a standard reference gas module; (d)calibrating the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes from eachof the analyzers based on the standard reference baseline; (e) sendingthe measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the forest airsamples to a data processing system; and (f) converting the measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes in the data processing system totradable products that separately quantify biogenic and fossil carbon inthe forest.
 12. The method of claim 11, wherein said standard referencebaseline is obtained at each analyzer.
 13. The method of claim 11,further comprising standardizing the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes in the forest air samples based on measured amounts of ¹²C,¹³C, and ¹⁴C isotopes in a global reference sample.
 14. The method ofclaim 13, wherein said global reference sample is located in asatellite.
 15. The method of claim 11, wherein at least 25 analyzers areplaced at predetermined representative locations throughout a forest.16. The method of claim 11, wherein at least 100 analyzers are placed atpredetermined representative locations throughout a forest.
 17. Themethod of claim 11, wherein amounts of ¹²C, ¹³C, and ¹⁴C isotopes in theforest air samples are collected and measured at a rate up to 100 Hz.18. The method of claim 11, wherein said predetermined representativelocations include borders of discrete forest areas, wherein said bordersinclude a region, a state, a group of states, a border configurationdefining a greenhouse gas treaty or other convention that requiresmonitoring greenhouse gases.
 19. The method of claim 11, wherein saidpredetermined representative locations include above the forest canopy,below the forest canopy and at the forest floor.
 20. The method of claim11, wherein said converting is carried out using one or more conversionsystems parameterized for biogenic and fossil carbon.
 21. A system ofsystems for generating tradable products that separately quantifybiogenic and fossil carbon in soil, comprising: (a) a carbon datacollection system for collecting carbon flux data from soil comprisingan array of analyzers placed at predetermined sub-surface locations,wherein each analyzer comprises a ¹²C laser device, a ¹³C laser device,a ¹⁴C laser device, (ii) a sample chamber to measure the individualamounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a soil sample, and atimer to allow measurements of ¹²C, ¹³C, and ¹⁴C isotopes at a rate ofat least 1 Hz; a standard reference module for obtaining a standardreference baseline and calibrating the measured amounts of the ¹²C, ¹³C,and ¹⁴C isotopes from each of said analyzers based on said standardreference baseline; and a telemetry device for sending measured amountsof ¹²C, ¹³C, and ¹⁴C isotopes to a data processing system; and (b) adata processing system for converting the measured amounts of ¹²C, ¹³C,and ¹⁴C isotopes to tradable products that separately quantify biogenicand fossil carbon in the soil.
 22. The system of systems of claim 21,wherein each analyzer comprises a standard reference gas module.
 23. Thesystem of systems of claim 21, further comprising a global referencesystem including a ¹²C laser device, a ¹³C laser device, a ¹⁴C laserdevice, and a global reference sample cell to measure the individualamounts of ¹²C, ¹³C and ¹⁴C isotopes contained in a global referencesample, and a calibration system for standardizing the measured amountof ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of said data collectionsystem based on said measured amounts of ¹²C, ¹³C, and ¹⁴C isotopescontained in the global reference sample.
 24. The system of systems ofclaim 23, wherein said global reference system is located in asatellite.
 25. The system of systems of claim 21, wherein said array ofanalyzers comprises more than 25 analyzers.
 26. The system of systems ofclaim 21, wherein said array of analyzers comprises more than 100analyzers.
 27. The system of systems of claim 21, wherein said timerallows measurements of ¹²C, ¹³C, and ¹⁴C isotopes at a rate up to 100Hz.
 28. The system of systems of claim 21, wherein said data processingsystem comprises one or more conversion systems parameterized forbiogenic and fossil fuel carbon to convert the measured amounts of ¹²C,¹³C, and ¹⁴C isotopes in the data processing system to tradable productsthat separately quantify biogenic and fossil carbon in the soil.
 29. Amethod for generating tradable products that separately quantifybiogenic and fossil carbon in soil, comprising: (a) placing an array ofanalyzers at predetermined representative sub-surface locations in soil,wherein each analyzer comprises a ¹²C laser device, a ¹³C laser device,a ¹⁴C laser device, and a sample chamber; (b) collecting in the samplechambers of the analyzers samples of carbon gas in soil and measuringthe individual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in thesamples at a rate of at least 1 Hz; (c) obtaining a standard referencebaseline with a standard reference module; (d) calibrating the measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes from each of the analyzers basedon the standard reference baseline; (e) sending the measured amounts of¹²C, ¹³C, and ¹⁴C isotopes in the soil samples to a data processingsystem; and (f) converting the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the soil.
 30. Themethod of claim 29, wherein said standard reference baseline is obtainedat each analyzer.
 31. The method of claim 29, further comprisingstandardizing the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in thesoil samples based on measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes ina global reference sample.
 32. The method of claim 31, wherein saidglobal reference sample is located in a satellite.
 33. The method ofclaim 29, wherein at least 25 analyzers are placed at predeterminedrepresentative locations throughout the soil.
 34. The method of claim29, wherein at least 100 analyzers are placed at predeterminedrepresentative locations throughout the soil.
 35. The method of claim29, wherein amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the soil samplesare collected and measured at a rate up to 100 Hz.
 36. The method ofclaim 29, wherein said converting is carried out using one or moreconversion systems parameterized for biogenic and fossil carbon.
 37. Themethod of claim 29, wherein the measured amount fossil carbon relativeto the measured biogenic carbon indicates damage in the soil.
 38. Asystem of systems for generating tradable products that separatelyquantify biogenic and fossil carbon in an agricultural area, comprising:(a) a carbon data collection system for collecting carbon flux data inan agricultural area comprising an array of analyzers placed atpredetermined representative above-ground and sub-surface locations inan agricultural area, wherein each analyzer comprises a ¹²C laserdevice, a ¹³C laser device, a ¹⁴C laser device, a sample chamber tomeasure the individual amounts of ¹²C, ¹³C, and ¹⁴C isotopes containedin the above-ground and sub-surface location samples, and a timer toallow measurements of ¹²C, ¹³C, and ¹⁴C isotopes at a rate of at least 1Hz; a standard reference module for obtaining a standard referencebaseline and calibrating the measured amounts of the ¹²C, ¹³C, and ¹⁴Cisotopes from each of said analyzers based on said standard referencebaseline; and a telemetry device for sending measured amounts of ¹²C,¹³C, and ¹⁴C isotopes to a data processing system; and (b) a dataprocessing system for converting the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes to tradable products that separately quantify biogenic andfossil carbon in the agricultural area.
 39. The system of systems ofclaim 38, wherein each analyzer comprises a standard reference gasmodule.
 40. The system of systems of claim 38, further comprising aglobal reference system including a ¹²C laser device, a ¹³C laserdevice, a ¹⁴C laser device, and a global reference sample cell tomeasure the individual amounts of ¹²C, ¹³C, and ¹⁴C isotopes containedin a global reference sample, and a calibration system for standardizingthe measured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers ofsaid data collection system based on said measured amounts of ¹²C, ¹³C,and ¹⁴C isotopes contained in the global reference sample.
 41. Thesystem of systems of claim 40, wherein said global reference system islocated in a satellite.
 42. The system of systems of claim 38, whereinsaid array of analyzers comprises more than 25 analyzers.
 43. The systemof systems of claim 38, wherein said array of analyzers comprises morethan 100 analyzers.
 44. The system of systems of claim 38, wherein saidabove-ground locations include 0 to 20 meters above the ground.
 45. Thesystem of systems of claim 38, wherein said sub-surface locationsinclude 0 to 100 meters below the surface.
 46. The system of systems ofclaim 38, wherein said timer allows measurements of ¹²C, ¹³C, and ¹⁴_(C isotopes at a rate up to) 100 Hz.
 47. The system of systems of claim38, wherein said data processing system comprises one or more conversionsystems parameterized for biogenic and fossil fuel carbon to convert themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the data processingsystem to tradable products that separately quantify biogenic and fossilcarbon in the agricultural area.
 48. The system of systems of claim 38,wherein said data processing system tracks the measured amounts of ¹²C,¹³C, and ¹⁴C isotopes over a period of time spanning from planting ofagricultural products, to growth of the agricultural products, and toharvesting of the agricultural products.
 49. A method for generatingtradable products that separately quantify biogenic and fossil carbon inan agricultural area, comprising: (a) placing an array of analyzers atpredetermined representative above-ground and sub-surface locations inan agricultural area, wherein each analyzer comprises a ¹²C laserdevice, a ¹³C laser device, a ¹⁴C laser device, and a sample chamber;(b) collecting in the sample chambers of the analyzers samples of carbongas in the above-ground and sub-surface locations and measuring theindividual amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in thesamples at a rate of at least 1 Hz; (c) obtaining a standard referencebaseline with a standard reference module; (d) calibrating the measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes from each of the analyzers basedon the standard reference baseline; (e) sending the measured amounts of¹²C, ¹³C, and ¹⁴C isotopes in the above-ground and sub-surface locationsamples to a data processing system; and (f) converting the measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes in the data processing system totradable products that separately quantify biogenic and fossil carbon inthe agricultural area.
 50. The method of claim 49, wherein said standardreference baseline is obtained at each analyzer.
 51. The method of claim49, further comprising standardizing the measured amounts of ¹²C, ¹³C,and ¹⁴C isotopes in the agricultural area samples based on measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes in a global reference sample. 52.The method of claim 51, wherein said global reference sample is locatedin a satellite.
 53. The method of claim 49, wherein at least 25analyzers are placed at predetermined representative locationsthroughout the agricultural area.
 54. The method of claim 49, wherein atleast 100 analyzers are placed at predetermined representative locationsthroughout the agricultural area.
 55. The method of claim 49, whereinsaid analyzers are placed 0 to 20 meters above the ground.
 56. Themethod of claim 49, wherein said analyzers are place 0 to 100 meterbelow the surface.
 57. The method of claim 49, wherein amounts of ¹²C,¹³C, and ¹⁴C isotopes in the above-ground and sub-surface locationsamples are collected and measured at a rate up to 100 Hz.
 58. Themethod of claim 49, wherein said converting is carried out using one ormore conversion systems parameterized for biogenic and fossil carbon.59. The method of claim 49, further comprising tracking the measuredamounts of ¹²C, ¹³C, and ¹⁴_(C isotopes over a period of time spanning from planting of agricultural products, to growth of the agricultural products, and to harvesting of the agricultural products.)60. A system of systems for generating tradable products that separatelyquantify biogenic and fossil carbon in a body of water, comprising: (a)a carbon data collection system for collecting carbon flux data from abody of water comprising an array of analyzers placed at predeterminedrepresentative locations across the body of water, wherein each analyzercomprises a gas stripping device capable of stripping dissolved gasesfrom the body of water, and a ¹²C laser device, a ¹³C laser device, a¹⁴C laser device, a sample chamber to measure the individual amounts of¹²C, ¹³C, and ¹⁴C isotopes in dissolved gas stripped from the body ofwater sample, and a timer to allow measurements of ¹²C, ¹³C, and ¹⁴Cisotopes at least once an hour; a standard reference gas module forobtaining a standard reference baseline and calibrating the measuredamounts of the ¹²C, ¹³C, and ¹⁴C isotopes from each of said analyzersbased on said standard reference baseline; and a telemetry device forsending measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes to a dataprocessing system; and (b) a data processing system for converting themeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes to tradable products thatseparately quantify biogenic and fossil carbon in the body of water. 61.The system of systems of claim 60, wherein each analyzer comprises astandard reference gas module.
 62. The system of systems of claim 60,further comprising a global reference system including a ¹²C laserdevice, a ¹³C laser device, a ¹⁴C laser device, and a global referencesample cell to measure the individual amounts of ¹²C, ¹³C, and ¹⁴Cisotopes contained in a global reference sample, and a calibrationsystem for standardizing the measured amount of ¹²C, ¹³C, and ¹⁴Cisotopes from the analyzers of said data collection system based on saidmeasured amounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in the globalreference sample.
 63. The system of systems of claim 62, wherein saidglobal reference system is located in a satellite.
 64. The system ofsystems of claim 60, wherein said array of analyzers comprises more than25 analyzers.
 65. The system of systems of claim 60, wherein said arrayof analyzers comprises more than 100 analyzers.
 66. The system ofsystems of claim 60, wherein said timer allows measurements of ¹²C, ¹³C,and ¹⁴C isotopes at a rate up to 100 Hz.
 67. The system of systems ofclaim 60, wherein said data processing system comprises one or moreconversion systems parameterized for biogenic and fossil fuel carbon toconvert the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the dataprocessing system to tradable products that separately quantify biogenicand fossil carbon in the body of water.
 68. The system of systems ofclaim 60, wherein said data processing system tracks the measuredamounts of ¹²C, ¹³C, and ¹⁴C isotopes over a period of time to monitorchange of nutrients in the body of water.
 69. A method for generatingtradable products that separately quantify biogenic and fossil carbon ina body of water, comprising: (a) placing an array of analyzers atpredetermined representative locations across the body of water, whereineach analyzer comprises a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, a sample chamber, and a gas stripping device capable ofstripping dissolved gases from the body of water; (b) collecting watersamples in the analyzers; (c) stripping dissolved gases from the watersamples; (d) collecting the gases in the sample chambers of theanalyzers and measuring the individual amounts of ¹²C, ¹³C, and ¹⁴Cisotopes contained in the samples at least once an hour; (e) obtaining astandard reference baseline with a standard reference gas module; (f)calibrating the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes from eachof the analyzers based on the standard reference baseline; (g) sendingthe measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the samples ofdissolved gases in the body of water to a data processing system; and(h) converting the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in thedata processing system to tradable products that separately quantifybiogenic and fossil carbon in the body of water.
 70. The method of claim69, wherein said standard reference baseline is obtained at eachanalyzer.
 71. The method of claim 69, further comprising standardizingthe measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the water samplesbased on measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in a globalreference sample.
 72. The method of claim 71, wherein said globalreference sample is located in a satellite.
 73. The method of claim 69,wherein at least 25 analyzers are placed at predetermined representativelocations throughout the body of water.
 74. The method of claim 69,wherein at least 100 analyzers are placed at predeterminedrepresentative locations throughout the body of water.
 75. The method ofclaim 69, wherein the water samples are collected and measured at a rateup to 100 Hz.
 76. The method of claim 69, wherein said converting iscarried out using one or more conversion systems parameterized forbiogenic and fossil carbon.
 77. The method of claim 69, furthercomprising tracking the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopesover a period of time to monitor change of nutrients in the body ofwater.
 78. A system of systems for generating tradable products thatseparately quantify biogenic and fossil carbon in flue gases,comprising: (a) a carbon data collection system for collecting carbonflux data from flue gases comprising an array of analyzers placed atpredetermined representative locations exposed to flue gases, whereineach analyzer comprises a ¹²C laser device, a ¹³C laser device, a ¹⁴Claser device, a sample chamber to measure the individual amounts of ¹²C,¹³C, and ¹⁴C isotopes contained in an air sample, and a timer to allowmeasurements of ¹²C, ¹³C, and ¹⁴C isotopes at least 1,440 times a day; astandard reference gas module for obtaining a standard referencebaseline and calibrating the measured amounts of the ¹²C, ¹³C, and ¹⁴Cisotopes from each of said analyzers based on said standard referencebaseline; and a telemetry device for sending measured amounts of ¹²C,¹³C, and ¹⁴C isotopes to a data processing system; and (b) a dataprocessing system for converting the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes to tradable products that separately quantify biogenic andfossil carbon in the flue gases.
 79. The system of systems of claim 78,wherein each analyzer comprises a standard reference gas module.
 80. Thesystem of systems of claim 78, further comprising a global referencesystem including a ¹²C laser device, a ¹³C laser device, a ¹⁴C laserdevice, and a global reference sample cell to measure the individualamounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in a global referencesample, and a calibration system for standardizing the measured amountof ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers of said data collectionsystem based on said measured amounts of ¹²C, ¹³C, and ¹⁴C isotopescontained in the global reference sample.
 81. The system of systems ofclaim 80, wherein said global reference system is located in asatellite.
 82. The system of systems of claim 78, wherein said array ofanalyzers comprises more than 25 analyzers.
 83. The system of systems ofclaim 78, wherein said array of analyzers comprises more than 100analyzers.
 84. The system of systems of claim 78, wherein said timerallows measurements of ¹²C, ¹³C, and ¹⁴ _(C isotopes at a rate up to)100 Hz.
 85. The system of systems of claim 78, wherein said dataprocessing system comprises one or more conversion systems parameterizedfor biogenic and fossil fuel carbon to convert the measured amounts of¹²C, ¹³C, and ¹⁴C isotopes in the data processing system to tradableproducts that separately quantify biogenic and fossil carbon in the fluegases.
 86. The system of systems of claim 78, wherein said dataprocessing system tracks the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes over a period of time to monitor reduction of combustion offossil carbon in accordance with regulatory or voluntary emissionguidelines.
 87. A method for generating tradable products thatseparately quantify biogenic and fossil carbon in flue gases,comprising: (a) placing an array of analyzers at predeterminedrepresentative locations exposed to flue gas, wherein each analyzercomprises a ¹²C laser device, a ¹³C laser device, a ¹⁴C laser device,and a sample chamber; (b) collecting in the sample chambers of theanalyzers samples of flue gas and measuring the individual amounts of¹²C, ¹³C, and ¹⁴C isotopes contained in the samples at least 1,440 timesa day; (c) obtaining a standard reference baseline with a standardreference gas module; (d) calibrating the measured amounts of ¹²C, ¹³C,and ¹⁴C isotopes from each of the analyzers based on the standardreference baseline; (e) sending the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes in the samples of flue gas to a data processing system; and(f) converting the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in thedata processing system to tradable products that separately quantifybiogenic and fossil carbon in the flue gases.
 88. The method of claim87, wherein said standard reference baseline is obtained at eachanalyzer.
 89. The method of claim 87, further comprising standardizingthe measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the flue gassamples based on measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in aglobal reference sample.
 90. The method of claim 89, wherein said globalreference sample is located in a satellite.
 91. The method of claim 87,wherein at least 25 analyzers are placed at predetermined representativelocations.
 92. The method of claim 87, wherein at least 100 analyzersare placed at predetermined representative locations.
 93. The method ofclaim 87, wherein the flue gas samples are collected and measured at arate up to 100 Hz.
 94. The method of claim 87, wherein said convertingis carried out using one or more conversion systems parameterized forbiogenic and fossil carbon.
 95. The method of claim 87, furthercomprising tracking the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopesover a period of time to monitor reduction of combustion of fossilcarbon in accordance with regulatory or voluntary emission guidelines.96. A system of systems for generating tradable products that separatelyquantify biogenic and fossil carbon near a nuclear power plant,comprising: (a) a carbon data collection system for collecting carbonflux data near a nuclear power plant comprising an array of analyzersplaced in predetermined representative locations near a nuclear powerplant, wherein each analyzer comprises a ¹²C laser device, a ¹³C laserdevice, a ¹⁴C laser device, a sample chamber to measure the individualamounts of ¹²C, ¹³C, and ¹⁴C isotopes contained in discharges of thenuclear power plant, and a timer to allow measurements of ¹²C, ¹³C, and¹⁴C isotopes at a rate of at least 1 Hz; a standard reference gas modulefor obtaining a standard reference baseline and calibrating the measuredamounts of the ¹²C, ¹³C, and ¹⁴C isotopes from each of said analyzersbased on said standard reference baseline; and a telemetry device forsending measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in the dischargesof the nuclear power plant to a data processing system; and (b) a dataprocessing system for converting the measured amounts of ¹²C, ¹³C, and¹⁴C isotopes to tradable products that separately quantify biogenic andfossil carbon near the nuclear power plant.
 97. The system of systems ofclaim 96, wherein each analyzer comprises a standard reference gasmodule.
 98. The system of systems of claim 96, further comprising aglobal reference system including a ¹²C laser device, a ¹³C laserdevice, a ¹⁴C laser device, and a global reference sample cell tomeasure the individual amounts of ¹²C, ¹³C, and ¹⁴C isotopes containedin a global reference sample, and a calibration system for standardizingthe measured amount of ¹²C, ¹³C, and ¹⁴C isotopes from the analyzers ofsaid data collection system based on said measured amounts of ¹²C, ¹³C,and ¹⁴C isotopes contained in the global reference sample.
 99. Thesystem of systems of claim 98, wherein said global reference system islocated in a satellite.
 100. The system of systems of claim 96, whereinsaid array of analyzers comprises more than 25 analyzers.
 101. Thesystem of systems of claim 96, wherein said array of analyzers comprisesmore than 100 analyzers.
 102. The system of systems of claim 96, whereinsaid timer allows measurements of ¹²C, ¹³C, and ¹⁴C isotopes at a rateof up to 100 Hz.
 103. The system of systems of claim 96, wherein saidpredetermined representative locations include locations near gaseousdischarge, solid discharge, liquid discharge, and combinations thereof.104. The system of systems of claim 1, wherein said data processingsystem comprises one or more conversion systems parameterized forbiogenic and fossil fuel carbon to convert the measured amounts of ¹²C,¹³C, and ¹⁴C isotopes in the data processing system to tradable productsthat separately quantify biogenic and fossil carbon in the discharges ofthe nuclear power plant.
 105. A method for creating generating tradableproducts that separately quantify biogenic and fossil carbon near anuclear power plant, comprising: (a) placing an array of analyzers atpredetermined representative locations throughout a nuclear power plant,wherein each analyzer comprises a ¹²C laser device, a ¹³C laser device,a ¹⁴C laser device, and a sample chamber; (b) collecting samples ofdischarges of the nuclear power plant in the sample chambers of theanalyzers and measuring the individual amounts of ¹²C, ¹³C, and ¹⁴Cisotopes contained in the samples at a rate of at least 1 Hz; (c)obtaining a standard reference baseline with a standard reference gasmodule; (d) calibrating the measured amounts of ¹²C, ¹³C, and ¹⁴Cisotopes from each of the analyzers based on the standard referencebaseline; (e) sending the measured amounts of ¹²C, ¹³C, and ¹⁴C isotopesin the samples of discharges of the nuclear power plant to a dataprocessing system; and (f) converting the measured amounts of ¹²C, ¹³C,and ¹⁴C isotopes in the data processing system to tradable products thatseparately quantify biogenic and fossil carbon in the discharge of thenuclear power plant.
 106. The method of claim 105, wherein said standardreference baseline is obtained at each analyzer.
 107. The method ofclaim 105, further comprising standardizing the measured amounts of ¹²C,¹³C, and ¹⁴C isotopes in the samples of discharges of the nuclear powerplant based on measured amounts of ¹²C, ¹³C, and ¹⁴C isotopes in aglobal reference sample.
 108. The method of claim 107, wherein saidglobal reference sample is located in a satellite.
 109. The method ofclaim 105, wherein at least 25 analyzers are placed at predeterminedrepresentative locations.
 110. The method of claim 105, wherein at least100 analyzers are placed at predetermined representative locations. 111.The method of claim 105, wherein amounts of ¹²C, ¹³C, and ¹⁴C isotopesin the samples of the discharges of the nuclear power plant arecollected and measured at a rate of up to 100 Hz.
 112. The method ofclaim 105, wherein said predetermined representative locations includelocations near gaseous discharge, solid discharge, liquid discharge, andcombinations thereof.
 113. The method of claim 105, wherein saidconverting is carried out using one or more conversion systemsparameterized for biogenic and fossil carbon.